Optical waveguides and methods thereof

ABSTRACT

Embodiments in accordance with the present invention provide waveguide structures and methods of forming such structures where core and laterally adjacent cladding regions are defined. Some embodiments of the present invention provide waveguide structures where core regions are collectively surrounded by laterally adjacent cladding regions and cladding layers and methods of forming such structures.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is a divisional of and claims the benefit of priorityunder 35 U.S.C. §120 from U.S. Ser. No. 10/579,763, filed Jan. 26, 2007,which is a national stage of PCT/US04/37188, filed Nov. 22, 2004, whichclaims the benefit of U.S. Provisional Applications No. 60/523,978,filed Nov. 21, 2003, and No. 60/585,235, filed Jul. 2, 2004. Thecontents of these applications are incorporated herein by reference intheir entirety.

TECHNICAL FIELD

The present invention relates generally optical waveguides and methodsof forming them.

BACKGROUND

Data transfer using optical frequency carrier waves generated by sourcessuch as lasers or light-emitting diodes is becoming increasinglyimportant. One means for conducting or guiding such optical frequencycarrier waves from one point to another is an optical waveguide. Opticalwaveguides encompass a first medium which is essentially transparent tothe light of the optical frequency carrier waves and a second mediumhaving a lower refractive index than that of the first medium. The firstmedium is surrounded by, or otherwise enclosed within, the secondmedium. Light introduced into an end of the first medium undergoes totalinternal reflection at the boundary with the second medium and thus isguided along an axis of the first medium Perhaps the most frequentlyused optical transport medium is glass formed into an elongated fiber.

However, while glass optical fibers are convenient for data transferover long distances, they are inconvenient for complex high-densitycircuitry because the high density of such circuitry makes their useproblematic and expensive. Polymeric materials, on the other hand, holdgreat promise for constructing cost effective, reliable, passive andactive integrated components capable of performing the requiredfunctions for integrated optics.

Therefore, considerable effort has been directed to forming opticalcoupling devices and more recently to optical waveguides that can beformed of polymeric materials using photohardenable techniques. Forexample, in U.S. Pat. No. 5,292,620, to Booth et al., waveguidestructures having a predetermined geometry and a process for formingthese structures using photohardenable techniques are disclosed. Thestructures of the '620 patent encompass at least one buried channelwaveguide in a laminated matrix where the waveguide and any connectingstructures are first formed in a photohardenable film detachablydisposed on a supporting substrate. After such first forming, thephotohardenable film is detached from the supporting substrate andlaminated between first and second photohardenable layers. In thismanner, regions of the photohardenable layer adjacent the waveguidechannel region and any connecting structures serve as cladding regionsin the plane of the layer and the first and second photohardenablelayers serve as cladding layers above and below that plane.

On the other hand, JP laid-open patent publications Nos. 2004-35838H10-48443 and 2001-296438 disclose a method of exposing a polymer filmto an actinic radiation, to change the chemical structure of the polymerso as to obtain a waveguide structure.

BRIEF DESCRIPTION OF THE DRAWINGS

Embodiments of the invention are described below with reference to thefollowing accompanying drawings.

FIGS. 1, 2 and 3 are schematic drawings that illustrate in a simplifiedmanner a sequence of forming waveguide regions in a waveguidepatternable film in accordance with an exemplary embodiment of thepresent invention;

FIGS. 4(A) and 4(B) are Electron Probe Microanalyses (EPMA) of astructure formed in the manner of the sequence depicted in FIGS. 1, 2and 3;

FIGS. 5, 6, 7, 8 and 9 are schematic drawings that illustrate in asimplified manner a sequence of forming waveguide regions in a waveguidepatternable film in accordance with another exemplary embodiment of thepresent invention;

FIG. 10 is a bar chart depicting the amount of energy output by atypical mercury vapor lamp at selected wavelengths within the UVspectrum and an overlaid absorption spectra of RHODORSIL® PHOTOINITIATOR2074 (available from Rhodia USA Inc., Cranbury, N.J.); and

FIG. 11 is a chart showing the total optical loss for propagation lossmeasurements.

DETAILED DESCRIPTION

Embodiments according to the present invention are describedhereinafter. Various modifications, adaptations or variations of suchexemplary embodiments described herein may become apparent to thoseskilled in the art as such are disclosed. It will be understood that allsuch modifications, adaptations or variations that rely upon theteachings of the present invention, and through which these teachingshave advanced the art, are considered to be within the scope and spiritof the present invention.

The term “norbornene-type monomer” is used herein to mean a monomermaterial that contains at least one norbornene moiety in accordancewith, for example, Structure A shown below, and the term“norbornene-type polymer” is used herein to mean a polymeric materialthat was formed from such monomers and that has at least one repeat unitin accordance with, for example, Structure B, also shown below:

The use of the term “norbornene-type monomer” herein further encompassespolycyclic olefins which can be polymerized via cationic palladiuminitiators that would lead to a propagating species in which there is nopossibility of beta-hydride elimination or equivalent terminationprocess, and the use of the term “norbornene-type polymer” hereinfurther encompasses polymeric materials that were formed from suchmonomers.

The terms “crosslinker” and “crosslinking monomer” are usedinterchangeably herein to mean a monomer that contains at least twonorbornene-type moieties such as shown above by ‘A’, each beingpolymerizable. Such crosslinkers include both fused multicyclic ringsystems and linked multicyclic ring systems, as will be described morefully below.

The terms “waveguide channel” or “core” refer to a portion of apolymeric film having a square or rectangular cross-sectional profilewith the dimensions of the square or rectangular cross-sectional profileranging from about 1 μm to about 200 μm in some embodiments, from about5 μm to about 100 μm in other embodiments and from about 10 μm to about60 μm in still other embodiments. Such waveguide channel or core regionsare further characterized as having a refractive index that is higherthan the refractive index of laterally adjacent regions which arereferred to as cladding regions. Optical waveguides according to theembodiments of the present invention can be used, for example, in datacommunication using a range of wavelengths, generally, but not limitedto, 600 nm to 1550 nm. Usually, the wavelengths of operation depend onmaterials and their optical characteristics.

Referring first to FIG. 1, a portion of a waveguide patternable film 10of a photo-induced thermally developable material (PITDM), in accordancewith embodiments of the present invention, is depicted as disposed on asupport substrate 5. Generally, substrate 5 is a silicon, silicondioxide, glass or quartz substrate, or a polyethylene terephthalate(PET) film.

The PITDM encompasses, for example, a norbornene-type polymeric materialmatrix 15 having a plurality of norbornene-type repeat units andmaterials 20 dispersed therein. Materials 20 may include, for example, aphotoinitiator material, a procatalyst material and a norbornene-typemonomer material. The term “photoinitiator material” will be understoodherein to include both cationic and anion photoinitiator materials whichare also referred to as “photo acid generators” and “photo basegenerators,” respectively. Generally, the PITDM of film 10 alsoencompasses one or more antioxidant materials to prevent undesirablefree radical generation and auto-oxidation of the norbornene-typematerials, although the inclusion of such antioxidants can be optionalwhere the PITDM is not subjected to oxidative conditions or where theperiod of such exposure is limited. Each of the materials 20 isessentially uniformly and randomly distributed within matrix 15. Thuswhen film 10 is formed, such materials 20 are essentially uniformly andrandomly distributed therein.

The PITDM is applied to substrate 5 to form film or layer 10 using anyone of several appropriate application methods. Such methods include,but are not limited to, spin coating, spray coating, dip coating andspreading with a doctor blade. In one exemplary embodiment of thepresent invention, a solution of the PITDM, also referred to herein as a“varnish” or a “varnish solution,” is poured onto a glass substrate andspread to an essentially uniform thickness using a doctor blade. In someembodiments of the present invention, the essentially uniform thicknessof the layer is from about 5 μm to about 200 μm, while in otherembodiments, layer 10 has a thickness of from about 10 μm to about 100μm and in still other embodiments, layer 10 has a thickness of fromabout 15 μm to about 65 μm. After spreading, the coated glass substrateis allowed to sit on a vented leveling table to allow for the levelingof surface irregularities resulting from the method of application aswell as to allow for solvent evaporation and the forming of a solidfilm, such as PITDM film 10 depicted in FIG. 1. It will be noted thatPITDM film 10 is created by spreading the varnish solution to anessentially uniform thickness, and that the materials 20 and matrix 15encompassed within such varnish solution are essentially uniformly andrandomly distributed within film 10.

Matrix 15 generally encompasses a polymer, for example, anorbornene-type polymer having two or more distinct norbornene-typerepeat units (hereinafter, the terms “first repeat units” and “secondrepeat units” herein are used to mean two distinct repeat units). Insome embodiments in accordance with the present invention, a polymerresulting from the polymerization of essentially equal amounts ofhexylnorbornene (HxNB) and diphenylmethyl norbornenemethoxysilane(diPhNB) results in a copolymer that is useful for matrix 15. However,while matrix 15 can encompass two or more distinct norbornene-typerepeat units, for some embodiments in accordance with the presentinvention, matrix 15 can be an appropriate norbornene-type homopolymer.It will be realized that the exemplary norbornene-type polymers andmonomers as described in the embodiments in accordance with the presentinvention can provide optical waveguides having excellent heat resistantcharacteristics. It will be further realized that the exemplarynorbornene-type polymers as described in the embodiments in accordancewith the present invention improve hydrophobicity, thus providing a filmwhich is less susceptible to water damage such as a size variation dueto water absorption. While the embodiments of the present invention aredescribed about the PITDM including norbornene-type polymers, thepresent invention does not limit to such polymers. For example, polymersfor the PITDM include ones which are sufficiently transparent orcolorless for the purposes of optical waveguide and which are compatiblewith monomers. The term “compatible” herein means that monomers are atleast miscible and create no phase separation in a polymer matrix. Forexample, other norbornene-type polymers such as those synthesized byvarious polymerization processes of the norbornene-type monomers, e.g.,Ring-Opening Metathesis Polymerization (ROMP), a combination of ROMP andhydrogenation, polymerization via radical or cation, andethylene-norbornene co-polymerization may be useful. Furthermore, othernorbornene-type polymers such as those synthesized by using initiatorsor catalysts other than cationic palladium initiators, for example,nickel and other transition metal initiators may be useful. Polymersother than the norbornene-type polymers include ones which aresufficiently transparent or colorless for the purposes of opticalwaveguide and which are compatible with monomers and which can functionas a matrix in which a monomer can be polymerized or crosslinked,and/or, in which a cleavable pendant group is included. Polymers as thematrix should be transparent when polymerizing the monomers in thematrix. Exemplary polymers are polyesters, polyacrylates,polymethacrylates, epoxides and polystyrenes, etc.

Matrix 15 may also include repeat units having a cleavable pendantgroup. The term “cleavable pendant group” means a pendant group thatincludes a moiety or site where the pendant group or at least a partthereof, is cleaved upon exposure to energy from an energy source, forexample, actinic radiation and/or thermal energy. Usually, a proton,anion or free radical interacts with the moiety, or at the site, toinitiate or cause the cleaving of the pendant group or at least its partfrom the matrix. Thus, embodiments in accordance with the presentinvention may have a “cleavable pendant group” that is an “acid (proton)cleavable pendant group,” a “base (anion) cleavable pendant group” or a“free radical cleavable pendant group.”

After being cleaved, the cleavable pendant group may be removed from thematrix, so as to change the refractive index. On the other hand, thecleavable pendant group may remain in the matrix, if it serves toprovide distinctive refractive indices between the exposed and unexposedregions. For example, the cleavable pendant group or at least a partthereof may be at least partially cleaved and cause rearrangement orcrosslinkage within the polymer matrix, thereby resulting in change inthe refractive index. The term “photo bleaching” is therefore used tomean any changes, whether increase or decrease, in the refractive indexof the polymer matrix when the cleavable pendent group is partly orpartially cleaved from the polymer matrix and is removed, rearranges orcrosslinks upon exposure to actinic radiation and/or thermal energy. Itwill be understood that the term “actinic radiation” is meant to includeany radiation capable of causing a photochemical type of reaction, andfurther includes, herein, electron beam radiation, x-rays and the like.

In some embodiments of the present invention, matrix 15 has a pendantgroup having a moiety of —O—, —Si-phenyl, or —OSi—. In other embodimentsof the present invention, matrix 15 has a pendant group having a moietyof —Si-diphenyl or —OSi-diphenyl. In other embodiments of the presentinvention, matrix 15 is a homopolymer or copolymer of a diPhNB monomer.

Materials 20 according to some embodiments of the present inventioninclude one or more distinct monomers where at least one of suchmonomers is a crosslinking monomer. An exemplary crosslinker founduseful is bis-(norbornenemethoxy) dimethylsilane (SiX).

A cocatalyst, also referred to as an activator, activates theprocatalyst, also referred to as an initiator. For example, suchactivation can encompass a cocatalyst providing a weakly coordinatinganion (hereinafter also referred to as “WCA”) where such WCA replaces aleaving group on the procatalyst Some exemplary WCAs aretetrakis(pentafluorophenyl)borate (FABA), SbF₆ ⁻,tetrakis(pentafluorophenyl)gallate, aluminates, antimonates, otherborates, gallates, carboranes and halocarboranes. According to someembodiments of the present invention, the cocatalyst decomposes uponexposure to actinic radiation of an appropriate wavelength to form, inpertinent part, a cation such as a proton, and the WCA for activatingthe procatalyst. Where the cleavable pendant group is provided, it canbe advantageous to select cationic or anionic photoinitiators havingsuch weakly coordinating anion of FABA⁻ or SbF₆ ⁻.

Exemplary materials useful in embodiments of the present invention areRHODORSIL® PHOTOINITIATOR 2074, CAS 178233-72-2, available from RhodiaUSA Inc., Cranbury, N.J. and TAG-372R photo acid generator, CAS193957-54-9, available from Toyo Ink Mfg. Co., Ltd., Tokyo, Japan.Additionally, MPI-103, CAS 87709-41-9, available from Midori Kagaku Co.,Ltd., Tokyo, Japan, TAG-371, CAS 193957-53-8, available from Toyo InkMfg. Co., Ltd., Tokyo, Japan, and tris(4-tertbutylphenyl)sulphoniumtetrakis(pentafluorophenyl)borate (also referred to as “TTBPS-TPFPB”),available from Toyo Gosei Co., Ltd., Tokyo, Japan.

While the embodiments of the present invention are described about theDM including specific photoinitiators (photo acid generators) forcocatalysts, the present invention does not limit to suchphotoinitiators. So long as the activating temperature for theprocatalyst (catalyst) is changed (e.g., raised or decreased) due toactinic radiation, or so long as the specific moiety in the pendantgroup of a matrix is cleaved due to actinic radiation, any cocatalystsor photoinitiators can be used.

When PITDM includes a procatalyst, generally such may be selected frommoieties represented by Formulae Ia and Ib:(E(R)₃)₂Pd(Q)₂  Ia; and[(E(R)₃)_(a)Pd(Q)(LB)_(b)]_(p)[WCA]_(r)  Ib.

In Formulae Ia and Ib, E(R)₃ represents a Group 15 neutral electrondonor ligand, where E is an element selected from Group 15 of thePeriodic Table of the Elements, R independently represents hydrogen (orone of its isotopes) or an anionic hydrocarbyl containing moiety, and Qis an anionic ligand selected from a carboxylate, thiocarboxylate, anddithiocarboxylate group. In Formula Ib, LB is a Lewis base, WCArepresents a weakly coordinating anion, a represents an integer of 1, 2,or 3, b represents an integer of 0, 1, or 2, where the sum of a+b is 1,2, or 3, and p and r are integers that represent the number of times thepalladium cation and the weakly coordinating anion are taken to balancethe electronic charge on the structure of Formula Ib. In an exemplaryembodiment, p and r are independently selected from an integer of 1 and2. One such exemplary procatalyst is Pd(PCy₃)₂(OAc)₂ (hereinafterreferred to as “Pd785”), where Cy is an abbreviation representing acyclohexyl moiety and Ac is an abbreviation representing an acetatemoiety. It will be realized that the exemplary procatalysts describedabove and in some embodiments in accordance with the present inventioncan polymerize norbornene-type monomers via addition polymerization,whereby producing polymers or polymeric materials having excellent heatresistant characteristics.

While the embodiments of the present invention are described about thePITDM including specific procatalysts, the present invention is notlimited to such procatalysts. So long as the activating temperature ischanged (e.g., raised or decreased) due to actinic radiation, anyprocatalysts can be used.

Where antioxidants are included in materials 20, Ciba® IRGANOX® 1076 andCiba® IRGAFOS® 168, available from Ciba Specialty Chemicals Corporation,Tarrytown, N.Y., have been found useful, although other appropriateantioxidants can also be used. Other exemplary antioxidants includeCiba® Irganox® 129, Ciba® Irganox® 1330, Ciba® Irganox® 1010, Ciba®Cyanox® 1790, Ciba® Irganox® 3114 and Ciba® Irganox® 3125.

Turning now to FIG. 2, a portion of a spread film 10 is shown. Afterbeing sufficiently dried, that is to say that essentially any solvent(s)used in a solution containing the PITDM have been evaporated, the spreadfilm 10 becomes essentially a dried solid film. The dried film 10 of thePITDM has a first Refractive Index (RI) where such first RI is afunction of the materials 20 uniformly dispersed in the matrix 15.

As depicted, regions 25 of the film 10 are exposed to actinic radiation30 through a masking element 35, where a source of the actinic radiation30 is selected based on the sensitivity of the cocatalyst, e.g., acationic photoinitiator, in materials 20 to such radiation. Whereappropriate, any suitable sensitizer may be included in the varnishsolutions of the present invention. The term “sensitizer” refers to aspecies that enhances the sensitivity of a photoinitiator to actinicradiation and decrease amount of time and/or energy required for itsreaction or decomposition and/or that changes a wavelength of actinicradiation to which the photoinitiator is most sensitive. Such suitablesensitizers include, but are not limited to, anthracenes (e.g., DBA(9,10-Dibutoxyanthracene; CAS 76275-14-4), xanthones and anthraquinones.In addition, depending upon a peak wavelength of absorption, otherclasses of sensitizers such as phenanthrenes, chrysenes, benzpyrenes,fluoranthenes, rubrenes, pyrenes, indanthrenes, thioxanthen-9-ones, andmixtures thereof may be suitably used. In some exemplary embodiments,suitable sensitizers include 2-isopropyl-9H-thioxanthen-9-one,4-isopropyl-9H-thioxanthen-9-one, 1-chloro-4-propoxythioxanthone,phenothiazine, and mixtures thereof. A typical amount of sensitizer isat least 0.01 percent by weight, in some cases at least 0.5 percent byweight, and in other cases at least 1 percent by weight of thecomposition of a varnish solution. The amount of a sensitizer present invarnish solutions according to the embodiments of the present inventionvaries between any of the values recited above. Where RHODORSIL® 2074 isemployed in the film 10, a mercury vapor lamp is used as an ultraviolet(UV) radiation source to provide sufficient energy below 300 nanometers(nm) to cause the decomposition of the Rhodorsil and provide the cationand WCA as mentioned above. Laterally adjacent to the exposed regions 25are unexposed regions 40 which are protected from the radiation 30 byopaque portions of the masking element 35 as depicted.

It will also be understood that while the masking element 35 is depictedas only having two openings for allowing the radiation 30 to passthrough to the regions 25 of the film 10, such a depiction issimplified, and the masking element 35 can be provided having a varietyof more complex patterns to define one or more optical waveguideelements and/or coupling devices. It should be noted that the region 25can also be exposed by using a laser radiation or other collimatedradiation sources, and in such case, it may be unnecessary to use anymasking element. Waveguides in accordance with the embodiments of thepresent invention can be used, for example, for data communicationapplications such as “On board Chip to Chip Interconnects;” OpticalSwitches; and a variety of optical backplane applications such asOptical Add Drop Multiplexers (OADM); Multiplexers and Demultiplexers;Arrayed Waveguide Gratings (AWG); Microelectro-mechanical Systems(MEMS), and Microoptoelectro-mechanical Systems (MOEMS). In addition,fabrication methods in accordance with the present invention are usefulto form diffraction gratings, holographic films, lenses, microlensarrays and lens cap structures. Thus, it will be realized that the typesof waveguide structures that can be made using the methods of thepresent invention are generally limited only by the availability of aphotomask having the pattern required by the application. However,regardless of the complexity of any pattern used to define opticalwaveguide elements, each exposed region 25 defined by such pattern willhave one or more unexposed regions 40 laterally adjacent thereto.

Upon exposure to the radiation 30, the cocatalyst in exposed regions 25reacts or decomposes, in response to the exposure, to release a proton,or other cation, and a weakly coordinating anion (WCA). The proton andWCA serve to cause the conversion of the procatalyst to an active butlatent catalyst in situ, that is to say within the exposed regions 25 ofthe film 10. It will be understood that referring to the procatalyst orcatalyst as “active but latent” or “latently active” means that absentany additional changes/reactions, for example, increase in temperature,such latent procatalyst or catalyst will not cause the polymerization ofthe norbornene-type monomers sufficient to form a functional or usefuloptical waveguide within the regions 25 at room temperature. Therefore,if storage is desired, the latent procatalyst will not cause thepolymerization of the norbornene-type monomers at a temperature of, forexample, about −40° C.

In some embodiments of the present invention, for the purpose ofobtaining the active but latent catalyst, a PITDM film is exposed toactinic radiation at an exposure energy of 0.1 J/cm² to 9 J/cm², or 0.5J/cm² to 5 J/cm². Typically, the PITDM film is exposed to such actinicradiation having a peak wavelength of between 200 nm to 450 nm, althoughother wavelengths can be useful, the other wavelength being a functionof the cocatalyst and/or sensitizer employed.

The active but latent catalyst has an activating temperature lower thanan activating temperature of the procatalyst. In some embodiments of thepresent invention, the active but latent catalyst has an activatingtemperature 10° C. to 80° C. lower than an activating temperature of theprocatalyst.

Turning to FIG. 3, the structure of FIG. 2 is shown after thermalcuring. That is to say, the structure of FIG. 2 is heated to a firsttemperature for a first period of time and then to a second temperature,higher than the first, for a second period of time. The firsttemperature is sufficient to cause the active but latent catalyst tobecome an active catalyst and cause polymerization of thenorbornene-type monomers within the regions 25. The second temperatureis sufficiently higher such that the cocatalyst is thermally decomposedor reacted and thus the procatalyst is activated within the unexposedregion.

In some embodiments of the present invention, monomers are polymerizedin the matrix to form another polymer distinct from the matrix polymer.In other embodiments of the present invention, monomers (crosslinkers)serve to crosslink the polymer matrix. In some other embodiments of thepresent invention, monomers are polymerized and form a branched polymerfrom a main chain or a pedant group of the matrix polymer.

Before any exposure to the actinic radiation 30, the PITDM film 10 has afirst refractive Index (RI). After such exposure and subsequent heating,exposed regions 25 have a second RI and the laterally adjacent unexposedregions 40 have a third RI, where the second RI and the third RI aredifferent from each other. As mentioned above, the norbornene-typemonomers employed in some embodiments of the present invention can beselected such that when they are polymerized within exposed regions 25,thus changing the RI of such exposed regions 25 from the first RI to thesecond RI. The term “selective polymerization” is therefore used to meanpolymerization of monomers within a polymer matrix in a selected regionupon exposure of that region to actinic radiation and thermal energy.Without wishing to be bound by theory, it is believed thatnorbornene-type monomers from unexposed regions 40 diffuse into exposedregions 25 and are polymerized therein, and that such diffusion ofmonomers from unexposed regions 40 to exposed regions 25 results in thechanging of the RI in regions 40 from the first RI to the third RI.Advantageously, this diffusion process is also believed to provideadditional monomer to exposed regions 25 for polymerization thus aidingin the RI change of such exposed regions as mentioned above.

In order to provide for a difference between the second RI and the thirdRI, matrix 15 generally has a refractive index that is different fromthat of the monomer. In some embodiments of the present invention,matrix 15 has a refractive index higher than that of the monomer.

It is believed that as a result of the diffusion, exposed regions 25have a concentration of the repeating units or units of the monomer orcrosslinker higher than that of unexposed regions 40.

Where the second RI of exposed regions 25 is lower than the third RI ofthe unexposed regions 40, such unexposed regions 40 serve as opticalwaveguide cores or channels and exposed regions 25 serve as laterallyadjacent cladding regions. Alternatively, where the second RI is higherthan the third RI, exposed regions 25 serve as optical waveguide coresor channels and the unexposed regions 40 serve as laterally adjacentcladding regions.

It should be noted that the thermal step described above is particularlyadvantageous when the first period of time is sufficient forpolymerization within regions 25 to be substantially complete. Inaddition, it is advantageous for the second temperature to besufficiently high to cause any remaining cocatalyst such as a cationicphotoinitiator to thermally decompose and form the same species aspreviously described being caused by the radiation 30. It is believed,again without wishing to be bound by theory of invention, that thissecond heating results not only in the polymerization of any residual,not yet polymerized, norbornene-type monomers within exposed regions 25,but also to cause the polymerization of any of such monomers remainingin unexposed regions 40. In this manner, heating to the secondtemperature serves to stabilize the resulting structure of opticalwaveguide channel (or core) having laterally adjacent cladding regions.If necessary, additional heating can be applied for furtherstabilization, and in such case, generally the additional heating iscarried out at a temperature 20° C. higher than the second heating.

In addition to this at least two step curing cycle, it is alsoadvantageous in some embodiments of the present invention to wait for aperiod of time of about 30 minutes to about 60 minutes before beginningthe first step of the thermal cure cycle of an exposed structure. Whileit is uncertain why this waiting period is advantageous, delaying thethermal cure may allow a more complete or uniform conversion of aprocatalyst to a latent catalyst, thus providing more uniformpolymerization within exposed region.

In some of the embodiments of the present invention, the protongenerated from the photoinitiator interacts with the moiety, or site, ofthe cleavable pendant group, such that cleaving of at least a portion ofsuch pendant group occurs. Without wishing to be bound by theory, it isbelieved that some or all of the pendant group are partly or entirelycleaved at the time of receiving appropriate exposure energy and/or atthe time of heating at an appropriate temperature.

Referring to some exemplary embodiments V21-25 and V51 in accordancewith the present invention, film 10 can include matrix 15 whichencompasses a homopolymer or a copolymer of diphenylmethylnorbornenemethoxysilane (diPhNB) and a photo acid generator, e.g.,RHODORSIL® PHOTOINITIATOR 2074. When this film is exposed to an actinicradiation through a photomask, a change or a reaction in the matrix 15is initiated in the region 25.

In the embodiments using matrix 15 of a norbornene-type polymer, for thepurpose of cleaving the cleavable pendant group, region 25 is exposed atan exposure energy of 1 J/cm² to 9 J/cm², and in particular, of 3 J/cm²to 6 J/cm². For example, region 25 can be exposed to an actinicradiation having a peak wavelength of between 200 nm to 450 nm.

After the exposure, the film is heated, and as a result, the refractiveindex changes in the exposed region 25. Without being bound by theory,it is believed that the cleaved pendant group is removed from the matrixwhen the film is heated. In view of forming a waveguide structure havingdistinct refractive index regions, in some embodiments the film isheated to a temperature of 70° C. or more, in other embodiments to atemperature of 85° C. or more. The upper limit of the temperature is afunction of the heat resistance of the film. In case of thenorbornene-type polymer, the upper limit is generally about 200° C.Therefore, for such films encompassing norbornene-type polymers, therange for the heating is generally from 70° C. to 195° C., andtypically, from 85° C. to 150° C.

Thus, in some embodiments in accordance with the present invention,unexposed regions 40 have a concentration of the pendant group higherthan that of exposed regions 25.

In the embodiments in accordance with the present invention, distinctrefractive indices within exposed regions 25 and unexposed regions 40can be obtained by either the effect of the selective polymerization orthe effect of the photo bleaching, or by the combined effect ofselective polymerization and photo bleaching. To obtain the effect ofthe selective polymerization according to some embodiments of thepresent invention, the PITDM includes a polymer matrix, a monomer, acocatalyst and a procatalyst, as discussed above. To obtain the effectof the photo bleaching, the PITDM includes a polymer matrix including acleavable pendant group and a photoinitiator, as discussed above. Toobtain both of these effects, the PITDM includes a monomer, and aprocatalyst, a polymer matrix including a cleavable pendant group and asuitable photoinitiator, as discussed above.

To obtain the effect of the selective polymerization, more than oneheating step is generally employed while for the effect of photobleaching, it is sufficient to apply only one heating step. It should benoted that even after the heating(s), the procatalyst, cocatalyst and/orresidue(s) thereof may remain in the resultant waveguide structure. Bythe effect of the selective polymerization, the effect of the photobleaching, or their combination as described in the embodiments of thepresent invention, optical waveguides can be provided by more simplifiedprocessing and in less time, for example, compared to glass opticalwaveguides.

Referring to FIGS. 4(A) and 4(B), Electron Probe Microanalyses (EPMA) ofa waveguide pattern formed in an exemplary film in accordance with thepresent invention is shown. For the purpose of enhancing the sensitivityof the EPMA, a crosslinker monomer SiX is used in the exemplary film,thus increasing silicon available for detection. On the upper portion ofthe EPMA, silicon concentration is mapped, and in each of the verticallyextending areas corresponding to unexposed regions, the siliconconcentration is reduced relative to the adjacent areas corresponding toexposed regions. It is possible and believed that such an EPMA is oneindication that some of the SiX monomer diffuse from unexposed regionsto exposed regions where the SiX monomer are polymerized.

In some embodiments according to the present invention, film 10 can beremoved from substrate 5 after formation of an optical waveguide, thatis to say, formation of core regions and laterally adjacent claddingregions, and film 10 can be laminated to or disposed on one or morelayers which serve as a cladding layer. Such a cladding layer can beselected or formed such that they have a refractive index (RI) similarto the RI of the laterally adjacent cladding regions of film 10.

FIGS. 5-9 sequentially show processes of forming a multilayered opticalwaveguide structure according to some embodiments of the presentinvention.

In FIG. 5, a first layer 110 of a first varnish solution is formed in anessentially uniform thickness on substrate 100. Generally, substrate 100is a film of glass, quartz, or polyethylene terephthalate (PET).

In some embodiments of the present invention, the first layer 110 has anessentially uniform thickness of about 5 μm to about 200 μm, about 10 μmto about 100 μm, or about 15 μm to about 65 μm. To spread a varnishsolution evenly on substrate, any appropriate coating methods includingthe ones discussed in the embodiments of FIGS. 1-3 above.

In FIG. 6, second layer 120 of a photo-induced thermally developablematerial (PITDM) is shown as disposed over first layer 110. Second layer120 can be formed over first layer 110 by spreading a second varnishsolution encompassing the PITDM using an appropriate spreading methodeven before substantially drying first layer 110.

It is believed that while layers 110 and 120 remain essentially distinctfrom one another, some intermixing of the varnish solutions of layers110 and 120 can occur at their interface in some embodiments accordingto the present invention. While not wishing to be bound by theory, it isbelieved that such intermixing of two varnish solutions can bebeneficial in enhancing adhesion between layers 110 and 120 when amultilayered optical waveguide structure is completed. To control suchintermixing as well as to maintain uniform spreading of first and secondvarnish solutions in a desired thickness, varnish solutions can havecertain viscosities. For example, in some embodiments of the presentinvention, first and second varnish solutions can have a viscosity ofabout 100 centipoise to about 10000 centipoise, a viscosity of about 150centipoise to about 5000 centipoise, or a viscosity of about 200centipoise to about 3500 centipoise. In some embodiments in accordancewith the present invention, second varnish solution can have a viscosityhigher than that of first varnish solution. In some embodiments of thepresent invention, layer 120 has an as-spread thickness of about 5 μm to200 μm, about 15 μm to 125 μm, or about 25 μm to about 100 μm.

Turning to FIG. 7, third layer 130 of a third varnish solution is shownas disposed over second layer 120, forming a three-layer waveguidestructure 200. Layer 130 is applied over layer 120 in a manner analogousto that of layer 120.

In some embodiments of the present invention, layer 130 has an as-spreadthickness of about 5 μm to 200 μm, about 10 μm to 100 μm, or about 15 μmto 65 μm. The three-layer structure is then heated to a temperature ofabout 25° C. to 40° C. for about 15 minutes to 60 minutes to allow atleast some of the solvent(s) in varnish solutions to evaporate.

In the three-layer structure 200 in FIG. 7, waveguides, that is to say,core regions and laterally adjacent cladding regions, are formed inlayer 120, in a manner analogous to regions 40 and regions 25 of layer10 above. However, in FIGS. 5-9, first and third layers 110 and 130 formcladding regions distinct from laterally adjacent cladding regions inlayer 120. Thus, in some embodiments as described in FIGS. 5-9 accordingto the present invention, cladding layers are not laminated to core orwaveguide layer. That is, while layers 110, 120 and 130 can be spreadwithout substantially drying, in some embodiments of the presentinvention, layers 110, 120 and 130 can be spread with some drying.

As previously described, layers 110, 120 and 130 can intermix at theirinterfaces to allow adhesion in a completed three-layer waveguidestructure. In some embodiments in accordance with the present invention,layers 110 and 130 can employ varnish solutions analogous to that oflayer 120. Thus, polymerization of monomers can take place in layers 110and 130, at their interfaces of layer 120, and/or across suchinterfaces.

Turning to FIG. 8, three-layer structure 200 is shown as being exposedto actinic radiation 300 through masking elements 350. Regions 150 areexposed to actinic radiation 300 through masking elements 350; butregions 140 are protected from such exposure by opaque portions ofmasking elements 350. Source of actinic radiation 300 is selected basedon the sensitivity of a cocatalyst, e.g., a cationic photoinitiator.Thus, where RHODORSIL® 2074 is employed in layer 120, a mercury vaporlamp is used as an ultraviolet (UV) radiation source to providesufficient energy below 300 nanometers (nm) to cause the decompositionof Rhodorsil and provide cation and WCA within exposed regions 150.

While masking element 350 shown in FIG. 8 has two openings through whichradiation 300 passes, masking element 350 can be have any patterns todefine one or more optical waveguide elements and/or coupling devices.

Referring to FIG. 9, the structure of FIG. 8 after thermal curing isshown. That is to say, the structure shown in FIG. 9 is first heated toa first temperature for a first period of time to allow removal of anyresidual solvents in structure 200, then second heated to a secondtemperature higher than the first temperature for a second period oftime, and finally third heated to a third temperature higher than thesecond temperature for a third period of time. The second temperature issufficient to cause an active but latent catalyst to become an activecatalyst and cause polymerization of norbornene-type monomers withinexposed regions 150. Without wishing to be bound by theory, it isbelieved that in addition to polymerization of norbornene-type monomerin regions 150 upon exposure to actinic radiation 300, norbornene-typemonomer diffuses into exposed regions 150 from unexposed regions 140 inlayer 120 and is polymerized therein. The exposure and thermal curing oflayers in structure 200 are analogous to those described in theembodiments of FIGS. 1-3. Thus, after the second heating, a waveguidepattern can be visible within structure 200 where one of the exposed andunexposed regions 150 and 140 is a core region and the other is alaterally adjacent cladding region.

While the second temperature can be sufficient for substantiallycomplete polymerization within regions 150, the third temperature can besufficiently high such that any remaining cocatalyst is thermallydecomposed and form the same species as the ones caused by radiation300. It is believed, again without wishing to be bound by theory, thatthe third heating results in polymerization of any residual, not yetpolymerized, monomers within exposed regions 150, and also causespolymerization of monomers remaining in unexposed regions 140. It willbe realized that the third temperature serves to stabilize a resultingoptical waveguide structure.

In some embodiments according to the present invention, layers 110 and130 can include a procatalyst, a polymer matrix, monomers and acocatalyst. Materials for layers 110 and 130 can be selected based onthe effects of the selective polymerization and photo bleaching. Whenlayers 110 and 130 are to serve as cladding layers, polymer matrices oflayers 110 and 130 can be different from polymer matrix employed forlayer 120. For example, where polymer matrix of layer 120 has arelatively high refractive index (RI), polymer matrices of layers 110and 130 can have a relatively low RI. Thus, layers 110 and 130 do notdevelop distinct core and cladding regions. In addition, monomer forsuch layers 110 and 130 can be the same monomer as that of layer 120 andcatalyst to monomer ratio in layers 110 and 130 can be adjusted to belower than that of layer 120. As such, polymer matrices of layers 110and 130 can have a refractive index which is the same as or similar tothat of monomers included therein, and still avoid formation of distinctcore and clad regions in layers 110 and 130. Also, in some embodimentsaccording to the present invention, layers 110 and 130 include a polymermatrix having repeat units without a cleavable pendant group, and/orinclude no photo acid generator, thereby avoiding the effect of thephoto-bleaching in layers 110 and 130. Without wishing to be bound bytheory, it is believed that monomer from layers 110 and 130 diffusesinto layer 120 and polymerizes to polymer chains in an adjacent layer.Adhesion between such adjacent layers can be enhanced. Other varnishsolutions for layers 110 and 130 are contemplated and/or have beenevaluated. For example, in some embodiments of the present invention,varnish solutions for layers 110 and 130 incorporate norbornene-typepolymers where at least one of norbornene-type repeat units encompassesa pendant group having an epoxide moiety, and an acid generatingmaterial, providing for opening of the epoxide moiety. Such varnishsolutions also improve adhesion between layers 110 and 130.

In some embodiments of the present invention, varnish solutions caninclude a norbornene-type polymer where at least one of its repeat unitsencompasses a pendant group having an epoxy moiety or TMSE(trimethoxysilylethyl) moiety group. An exemplary norbornene-typepolymer is a copolymer of Hexyl Norbornene (HxNB) andnorbornenemethylglycidylether (AGENB) and an exemplary varnish solutionincludes such a HxNB/AGENB copolymer and an acid generator materialsuitable for causing its epoxy moiety to open. Such a varnish solutionprovides excellent adhesion to a waveguide layer with core and laterallyadjacent cladding regions. In some embodiments, acid generator materialcan be a photoinitiator such as RHODORSIL 2074 or TAG-372R which issuitable for opening an epoxy moiety during formation of an adjacentwaveguide layer. In some embodiments according to the present invention,acid generator material can be selected such that an epoxy moiety can beopened independently from formation of an adjacent waveguide layer. Forexample, an acid generator can be selected such that it does not absorbactinic radiation appropriate for a cocatalyst in a waveguide layer orit is thermally activated rather than photonically activated. In someembodiments according to the present invention, a non-absorbingphoto-base generator (PBG) or a thermal-base generator (TBG) can be usedin a varnish solution. Such generators can also provide opening of anepoxy moiety.

As described above, a three-layer waveguide structures can be formed insome embodiments of the present invention using varnish solutionsencompassing norbornene-type repeat units with an epoxy moiety.

Monomers

As discussed above, a monomer can be included in the PITMD. In someembodiments in accordance with the present invention, the monomer caninclude norbornene-type monomers. For example, the norbornene-typemonomers in accordance with the present invention may be represented byStructure C below:

wherein “a” represents a single or double bond, R¹ to R⁴ independentlyrepresent a hydrogen, hydrocarbyl or functional substituent, m is aninteger from 0 to 5, and when “a” is a double bond, one of R¹, R² andone of R³, R⁴ are not present.

When the substituent is a hydrocarbyl group, R¹ to R⁴ can be ahalohydrocarbyl, or perhalohydrocarbyl group, or even a perhalocarbylgroup (e.g., a trifluoromethyl group). In one embodiment, R¹ to R⁴independently represent hydrocarbyl, halogenated hydrocarbyl andperhalogenated hydrocarbyl groups selected from hydrogen, linear orbranched C₁-C₁₀ alkyl, linear or branched C₂-C₁₀ alkenyl, linear orbranched C₂-C₁₀ alkynyl, C₄-C₁₂ cycloalkyl, C₄-C₁₂ cycloalkenyl, C₆-C₁₂aryl, and C₇-C₂₄ aralkyl, R₁ and R₂ or R₃ and R₄ can be taken togetherto represent a C₁-C₁₀ alkylidenyl group. Representative alkyl groupsinclude but are not limited to methyl, ethyl, propyl, isopropyl, butyl,isobutyl, sec-butyl, tert butyl, pentyl, neopentyl, hexyl, heptyl,octyl, nonyl, and decyl. Representative alkenyl groups include but arenot limited to vinyl, allyl, butenyl, and cyclohexenyl. Representativealkynyl groups include but are not limited to ethynyl, 1-propynyl,2-propynyl, 1-butynyl, and 2-butynyl. Representative cycloalkyl groupsinclude but are not limited to cyclopentyl, cyclohexyl, and cyclooctylsubstituents. Representative aryl groups include but are not limited tophenyl, naphthyl, and anthracenyl. Representative aralkyl groups includebut are not limited to benzyl, and phenethyl. Representative alkylidenylgroups include methylidenyl, and ethylidenyl groups.

In one embodiment, the perhalohydrocarbyl groups include perhalogenatedphenyl and alkyl groups. The halogenated alkyl groups useful in theembodiment of invention are partially or fully halogenated and arelinear or branched, and have the formula C_(z)X″_(2z+1) wherein X″ isindependently a halogen or a hydrogen and z is selected from an integerof 1 to 20. In another embodiment, each X″ is independently selectedfrom hydrogen, chlorine, fluorine and/or bromine. In yet anotherembodiment, each X″ is independently either a hydrogen or a fluorine.

In another embodiment, the perfluorinated substituents includeperfluorophenyl, perfluoromethyl, perfluoroethyl, perfluoropropyl,perfluorobutyl, and perfluorohexyl. In addition to the halogensubstituents, the cycloalkyl, aryl, and aralkyl groups of the inventioncan be further substituted with linear or branched C₁-C₅ alkyl andhaloalkyl groups, aryl groups and cycloalkyl groups.

When the pendant group(s) is(are) a functional substituent, R¹ to R⁴independently represent a radical selected from(CH₂)_(n)—CH(CF₃)₂—O—Si(Me)₃, —(CH₂)_(n)—CH(CF₃)₂—O—CH₂—O—₃,(CH₂)_(n)—CH(CF₃)₂—O—C(O)—O—C(C₃)₃, —(CH₂)_(n)—C(CF₃)₂—OH,(CH₂)_(n)C(O)NH₂, (CH₂)_(n)C(O)Cl, (CH₂)_(n)C(O)OR⁵, (CH₂)n-OR⁵,—(CH₂)_(n)—OC(O)R⁵, (CH₂)_(n)C(O)R⁵, (CH₂)_(n)—OC(O)OR⁵,(CH₂)_(n)Si(R⁵)₃, —(CH₂)_(n)Si(OR⁵)₃, —(CH₂)_(n)—O—Si(R⁵)₃, and(CH₂)_(n)C(O)OR⁶ wherein n independently represents an integer from 0 to10 and R⁵ independently represents hydrogen, linear or branched C₁-C₂₀alkyl, linear or branched C₁-C₂₀ halogenated or perhalogenated alkyl,linear or branched C₂-C₁₀ alkenyl, linear or branched C₂-C₁₀ alkynyl,C₅-C₁₂ cycloalkyl, C₆-C₁₄ aryl, C₆-C₁₄ halogenated or perhalogenatedaryl, and C₇-C₂₄ aralkyl. Representative hydrocarbyl groups set forthunder the definition of R⁵ are the same as those identified above underthe definition of R¹ to R⁴. As set forth above under R¹ to R⁴ thehydrocarbyl groups defined under R⁵ can be halogenated andperhalogenated. For example, when R⁵ is C₁-C₂₀ halogenated orperhalogenated alkyl, R⁵ can be represented by the formulaC_(z)X″_(2z+1), wherein z and X″ are defined as above, and at least oneX″ on the alkyl group must be a halogen (e.g., Br, Cl, or F). It is tobe recognized that when the alkyl group is perhalogenated, all X″substituents are halogenated. Examples of perhalogenated alkyl groupsinclude, but are not limited to, trifluoromethyl, trichloromethyl,—C₇F₁₅, and —C₁₁F₂₃. Examples of perhalogenated aryl groups include, butare not limited to, pentachlorophenyl and pentafluorophenyl. The R⁶radical represents an acid labile moiety selected from —C(CH₃)₃,—Si(CH₃)₃, CH(R⁷)OCH₂CH₃, —CH(R⁷)OC(CH₃)₃ or the following cyclicgroups:

wherein R⁷ represents hydrogen or a linear or branched (C₁-C₅) alkylgroup. The alkyl groups include methyl, ethyl, propyl, i-propyl, butyl,i butyl, t butyl, pentyl, t-pentyl and neopentyl. In the abovestructures, the single bond line projecting from the cyclic groupsindicates the position where the cyclic protecting group is bonded tothe acid substituent. Examples of R6 radicals include1-methyl-1-cyclohexyl, isobornyl, 2-methyl-2-isobornyl,2-methyl-2-adamantyl, tetrahydrofuranyl, tetrahydropyranoyl,3-oxocyclohexanonyl, mevalonic lactonyl, 1-ethoxyethyl, and 1-t-butoxyethyl.

The R⁶ radical can also represent dicyclopropylmethyl (Dcpm), anddimethylcyclopropylmethyl (Dmcp) groups which are represented by thefollowing structures:

In some embodiments of the present invention, the monomers discussedabove can be polymerized and employed as polymer matrix forphoto-induced thermally developable materials (PITDM). To obtain polymermatrix with a relatively high RI, monomers having aromatic, nitrogen, Bror Cl moieties can be generally selected and polymerized. On the otherhand, to obtain polymer matrix with a relatively low RI, monomers havingalkyl, F and/or ether moieties can be generally selected andpolymerized. In addition, the monomers discussed above can be employedfor norbornene-type monomers in preparing varnish solutions in someembodiments according to the present invention.

While the embodiments of the present invention are described about thePITDM including norbornene-type monomers, the present invention is notlimited to such monomers. Hence, monomers other than the norbornene-typemonomers are also within the scope and spirit of the present invention.Such monomers include those which can be polymerized or crosslinkedusing polymerization methods exemplified herein, or by means of anyappropriate addition polymerization method and/or ring-openingpolymerization method. Exemplary monomers include acrylates,methacrylates, epoxides, styrenes, etc.

Crosslinking Monomers

In addition to the norbornene-type monomers represented by Structure C,a “crosslinking monomer” can be also employed. In some embodiments, suchcrosslinking monomers can be norbornene-type monomers. For example,crosslinked polymers can be prepared by copolymerizing thenorbornene-type monomer(s) set forth under Structure C above with amultifunctional norbornene-type crosslinking monomer. By multifunctionalnorbornene-type crosslinking monomer is meant that the crosslinkingmonomer contains at least two norbornene-type moieties (norbornene-typedouble bonds), each functionality being polymerizable in the presence ofthe catalyst system of the present invention. The crosslinkable monomersinclude fused multicyclic ring systems and linked multicyclic ringsystems. Examples of fused crosslinking agents are illustrated instructures below. For brevity, norbornadiene is included as a fusedmulticyclic crosslinking agent and is considered to contain twopolymerizable norbornene-type double bonds. Crosslinking monomersprovide at least one of the following benefits: crosslinking monomerspolymerize faster, thus shortening process; they are less susceptible toevaporation during heating steps, thereby suppressing vapor-pressure;and they improve heat-resistance of optical waveguides.

wherein Y represents a methylene (—CH₂—) group and m independentlyrepresents an integer from 0 to 5, and when m is 0, Y represents asingle bond. Representative monomers under the forgoing formulae are setforth below.

A linked multicyclic crosslinking agent is illustrated generically bythe following structure:

wherein “a” independently represents a single or double bond, mindependently is an integer from 0 to 5, R⁹ is a divalent radicalselected from divalent hydrocarbyl radicals, divalent ether radicals anddivalent silyl radicals, and n is equal to 0 or 1. By divalent is meantthat a free valence at each terminal end of the radical is attached to anorbornene-type moiety. In one embodiment, the divalent hydrocarbylradicals are alkylene radicals and divalent aromatic radicals. Thealkylene radicals are represented by the formula —(C_(d)H_(2d))— where drepresents the number of carbon atoms in the alkylene chain and is aninteger from 1 to 10. The alkylene radicals are, in one embodiment,selected from linear or branched (C₁ to C₁₀) alkylene such as methylene,ethylene, propylene, butylene, pentylene, hexylene, heptylene, octylene,nonylene, and decylene. When branched alkylene radicals arecontemplated, it is to be understood that a hydrogen atom in thealkylene backbone is replaced with a linear or branched (C₁ to C₅) alkylgroup.

The divalent aromatic radicals are selected from divalent phenyl, anddivalent naphthyl radicals. The divalent ether radicals are representedby the group—R₁₀—O—R₁₀—,wherein R¹⁰ independently is the same as R⁹. Examples of specific linkedmulticyclic crosslinking agents are represented as the followingstructures:

In one embodiment, the crosslinking agent is selected from those shownbelow:

which is dimethyl bis[bicyclo[2.2.1]hept-2-ene-5-methoxy]silane (alsoreferred to herein as dimethyl bis(norbornene methoxy) silane or SiX),

where n is 0 to 4,

Some other types of norbornene-based crosslinking agents include, butare not limited to, those represented in the formulae below.

where m and n, if present in the formulae above, are independently aninteger from 1 to 4.

In another embodiment, fluorine-containing norbornene-based crosslinkersare used. For example, in one embodiment one or more of the followingfluorinated norbornene crosslinking agents can be utilized:

It should be realized that monomers useful for embodiments in accordancewith the present invention are not limited to the above. Also, exemplarymonomers, as listed above, may be used alone or in combination.

After forming the polymer matrix having the desired RI, a solution ofsuch matrix polymer and other materials is prepared. As mentioned above,the other materials include, but are not limited to, one or moredistinct monomers, procatalyst and cocatalyst, for example,norbornene-type monomers where at least one of such monomers is acrosslinking norbornene-type monomer, a cationic photoinitiator and,where desired, an antioxidant as described above. The RI of suchsolution is either higher or lower than that of polymer matrix. Monomersselected for a varnish solution are a function of a relative RI ofregions to be exposed. Thus in some embodiments of the presentinvention, where a relatively high RI is desired for an exposed region,a polymer matrix with a relatively low RI can be employed together withmonomers which give rise to a relatively high RI when polymerized.However, in forming one or more waveguide cores and laterally adjacentcladding regions, any other combinations of polymer matrix and at leastone monomer can be employed to obtain different refractive indices inexposed and unexposed regions.

The terms “high,” “relatively high,” “low,” “relatively low” do notrefer to absolute values of RI. Rather such terms are merely indicativeof refractive indices of regions, polymers or materials relative to oneanother. That is to say, a material or polymer is said to have a “high”or “relatively high” RI when compared to another material, polymer orregion having a lower RI.

Procatalysts

As mentioned above, some embodiments in accordance with the presentinvention use procatalyst moieties represented by Formulae Ia and Ib:(E(R)₃)₂Pd(Q)₂  Ia; and[(E(R)₃)_(a)Pd(Q)(LB)_(b)]_(p)[WCA]_(r)  Ib.In Formulae Ia and Ib, R, E, Q and LB are as previously defined.Exemplary procatalysts in accordance with formula Ia include, but arenot limited to Pd(P-i-Pr₃)₂(OAc)₂, Pd(PCy₃)₂(OAc)₂, Pd(PCy₃)₂(O₂CCMe₃)₂,Pd(PCp₃)₂(OAc)₂, Pd(PCy₃)₂(O₂CCF₃) and Pd(PCy₃)₂(O₂CC₆H₅)₃, where Cp iscyclopentyl and Cy is cyclohexyl.

The following procatalyst synthesis examples C₁ to C₄ demonstrate thepreparation of several exemplary procatalysts useful in embodiments ofthe present invention.

Example C1 Preparation of Pd(OAc)₂(P(i-Pr)₃)₂

In a N₂ filled flask equipped with an addition funnel, a CH₂Cl₂ solution(20 mL) of P(i-Pr)₃ (8.51 mL, 44.6 mmol) was added drop-wise to a −78°C. stirring reddish brown suspension of Pd(OAc)₂ (5.00 g, 22.3 mmol) inCH₂Cl₂ (30 mL). The suspension gradually cleared to a yellow greensolution which was allowed to warm to room temperature, stirred for twohours and then filtered through a 0.45 μm filter. Concentration of thefiltrate to approximately 10 mL followed by addition of hexanes (20 mL)afforded yellow solids which were filtered off (in air), washed withhexanes (5×5 mL) and dried in vacuo. Yield 10.937 g (89%). NMR data: ¹HNMR (δ, CD₂Cl₂): 1.37 (dd, 36H, CHCH₃), 1.77 (s, 6H, CCH₃), 2.12 (m, 6H,CH). ³¹P NMR (δ, CD₂Cl₂): 32.9 (s).

Example C2 Preparation of Pd(OAc)₂(P(Cy)₃)₂

In a two-neck round bottom flask equipped with an addition funnel, areddish brown suspension of Pd(OAc)₂ (5.00 g, 22.3 mmol) in CH₂Cl₂ (50mL) was set to stir at −78° C. The addition funnel was charged with aCH₂Cl₂ solution (30 mL) of P(Cy)₃ (13.12 g, 44.6 mmol) which was thenadded drop-wise to the stirring suspension over the course of 15 minutesresulting in a gradual change from reddish brown to yellow. After 1 hourof stirring at −78° C. the suspension was allowed to warns to roomtemperature, stiffed for an additional two hours and then diluted withhexanes (20 mL). The yellow solids were then filtered off in air, washedwith pentane (5×10 mL) and dried in vacuo. A second crop was isolated bycooling the filtrate to 0° C. and filtering, washing and drying aspreviously described. Yield 15.42 g (88%). NMR data: 1H NMR (δ, CD₂Cl₂):1.18-1.32 (br m, 18H, Cy), 1.69 (br m, 18H, Cy), 1.80 (br m, 18H, Cy)1.84 (s, 6H, CH₃), 2.00 (br d, 12H, Cy), 31P NMR (δ, CD₂Cl₂): 21.2 (s).

Example C3 Preparation of trans-Pd(O₂C-t-Bu)₂(P(Cy)₃)₂

Pd(O₂C-t-Bu)₂ (1.3088 g, 4.2404 mmol) was dispersed in CH₂Cl₂ (10 mL) ina 100 mL Schlenk flask, the contents of the flask was cooled to −78° C.and stirred. To the above solution was slowly added the CH₂Cl₂ (15 mL)solution of P(Cy)₃ (2.6749 g, 9.5382 mmol) via a syringe, stirred for anhour at −78° C. and at room temperature for 2 hours. Hexane (20 mL) wasadded to the above reaction mixture to give the title complex as ayellow solid (1.391 g). The solid was filtered, washed with hexane (10mL) and dried under reduced pressure. Solvent was removed from thefiltrate to give an orange solid which was then dissolved inCHCl₃/hexane mixture (1/1:v/v) and the resulting solution was evaporatedinside a fume hood to give more of the title complex (648 mg). Totalyield=2.039 g (2.345 mmol), 55.3%. Analysis Calc'd for C₄₆H₈₄O₄P₂Pd: C,63.54, H, 9.74%.

Example C4 Preparation of Pd(OAc)₂(P(Cp)₃)₂

In a N₂ filled flask, a reddish brown suspension of Pd(OAc)₂ (2.00 g,8.91 mmol) in CH₂Cl₂ (˜25 mL) was set to stir at −78° C. With a cannula,P(Cp)₃ (4.25, 17.83 mmol) in CH₂Cl₂ (˜20 mL) was added drop wise to thestirring suspension over the course of 10 minutes resulting in a gradualchange from orange brown to yellow. The suspension was allowed to warmto room temperature and stirred for an additional 1 hour. Concentrationof the solvent (˜5 mL) followed by addition of hexanes (˜15 mL) affordedyellow solids which were filtered off in air, washed with hexanes (5×10mL) and dried in vacuo. A second crop was isolated by cooling thefiltrate to 0° C. and filtering, washing, and drying as set forth inExample 3. Yield 4.88 g (85%). NMR data: ¹H NMR (δ, CD₂Cl₂): 1.52-1.56(br m, 12H, Cp₃), 1.67-1.72 (br m, 12H, Cp₃), 1.74 (s, 6H, CH₃),1.85-1.89 (br m, 12H, Cp₃), 1.96-1.99 (br d, 6H, Cp₃), 2.03-2.09 (br m,12H, Cp₃), 31P NMR (δ, CD₂Cl₂): 22.4 (s).

Polymers

Examples P1-P6, P8 and P9

Examples P1-P6, P8 and P9 demonstrate the synthesis of norbornene-typepolymers useful as matrix polymers in accordance with embodiments of thepresent invention.

Example P1 Synthesis of Hexyl Norbornene (HxNB)/DiphenylmethylNorbornenemethoxy Silane (diPhNB) Copolymer (P1)

HxNB (8.94 g, 0.05 mol), diPhNB (16.1 g, 0.05 mol), 1-hexene (4.2 g,0.05 mol) and toluene (142.0 g) were combined in a 250 mL serum bottleand heated to 120° C. in an oil bath to form a solution. To thissolution were added[Pd(PCy₃)₂(O₂CCH₃)(NCCH₃)]tetrakis(pentafluorophenyl)borate (Pd1446)(5.8E-3 g, 4.0E-6 mol) and N,N-dimethylaniliniumtetrakis(pentafluorophenyl)borate (DANFABA) (3.2E-3 g, 4.0E-6 mol), eachin the form of a concentrated dichloromethane solution. After addition,the resulting mixture was maintained at 120° C. for 6 hours. Thecopolymer was precipitated by adding methanol drop wise into thevigorously stirred reaction mixture. The precipitated copolymer wascollected by filtration and dried in an oven at 80° C. under vacuum.After drying, 12.0 g was obtained (48%). The molecular weight of thecopolymer was determined by GPC in THF solvent (polystyrene standard) tobe Mw=16,196 and Mn=8,448. The composition of the copolymer wasdetermined by 1H-NMR to be 54/46 HxNB/diPhNB. The refractive indices ofthis polymer were measured by prism coupling method and determined to be1.5569 in TE mode and 1.5555 in TM mode at a wavelength of 633 nm. Thedried copolymer was dissolved in sufficient mesitylene to result in a 10wt % copolymer solution.

Example P2 Synthesis of Hexyl Norbornene/Phenethyl Norbornene Copolymer(P2)

HxNB (2.78 g, 0.0156 mol), Phenyl ethyl norbornene (PENB, CAS29415-09-6) (7.22 g, 0.036 mol), 1-hexene (2.18 g, 0.026 mol) andtoluene (57.0 g) were combined in a 250 mL serum bottle and heated to120° C. in an oil bath. To this solution were added Pd1446 (3.0E-3 g,2.1E-6 mol) and DANFABA (6.7E-3 g, 8.4E-6 mol) in concentrated solutionsof dichloromethane. After addition, the resulting mixture was maintainedat 120° C. for 1 hour. After cooling to room temperature, the copolymerwas precipitated by adding methanol drop wise into the reaction mixture.The solid copolymer was collected by filtration and dried at 80° C. in avacuum oven. The solid polymer was dissolved in an appropriate amount ofmesitylene to give 10 wt % solid copolymer solution. After drying, 8.0 gwas obtained (80%). The molecular weight of the polymer was determinedby GPC methods in THF (poly(styrene) standard) Mw=127,332; Mn=39,206.The composition of the polymer was determined by ¹H-NMR:HxNB/PENB=22/78. The composition of the copolymer was determined by1H-NMR to be 54/46 HxNB/diPhNB. The refractive indices of this polymerwere measured by prism coupling method and determined to be 1.5601 in TEmode and 1.5585 in TM mode at a wavelength of 633 nm. The driedcopolymer was dissolved in sufficient mesitylene to result in a 10 wt %copolymer solution.

Example P3 Synthesis of HxNB/diPhNB Copolymer (P3)

HxNB (8.94 g, 0.050 mol), diPhNB (16.1 g, 0.050 mol), 1-hexene (2.95 g,0.035 mol) and toluene (142 g) were weighed out in a 250 mL serum bottleand heated at 80° C. in an oil bath. To this solution were added (5.8E-3g, 4.0E-6 mol) of Pd1446 and (3.2E-3 g, 4.0E-6 mol) of DANFABA. Theratio of norbornene monomers/Pd1446/DANFABA was 25K/1/1. The mixture wasmaintained at 80° C. for 7 h after which the activity of the Pd catalystwas quenched by adding 20 mL of acetonitrile. Thereafter, the polymerwas precipitated by adding methanol drop-wise to the reaction mixture.The precipitated copolymer was collected by filtration and dried at 65°C. in a vacuum oven. Then the copolymer was dissolved in mesitylene togive 10 wt % solid copolymer solution. After drying, 19.8 g was obtained(79%). The polymer's molecular weight was determined by GPC methods inTHF using poly(styrene) as a standard: Mw=86,186; Mn=21,602. The ratioof HxN2B/diPhNB in the polymer was determined by ¹-NMR:HxNB/diPhNB=46/54. The refractive indices of this polymer were measuredby prism coupling method and determined to be 1.5569 in TE mode and1.5556 in TM mode at a wavelength of 633 nm. The Tg (based onthermomechanical analysis (TMA) measurement) of this polymer was 203° C.The dried copolymer was dissolved in sufficient mesitylene to result ina 10 wt % copolymer solution.

Example P4 Synthesis of HxNB/diPhNB Copolymer (P4)

HxNB (8.94 g, 0.050 mol), diPhNB (16.1 g, 0.050 mol), 1-hexene (20.0 g,0.239 mol) and toluene (142 g) were weighed out into a 250 mL serumbottle and heated at 80° C. in an oil bath to form a solution. To thissolution were added Pd1446 (5.80E-3 g, 4.0E-6 mol) and DANFABA (3.21E-3g, 4.01E-6 mol). The mixture was maintained at 80° C. for 6 h afterwhich the activity of the Pd catalyst was quenched by adding 20 mL ofacetonitrile. Thereafter, the polymer was precipitated by addingmethanol drop-wise to the reaction mixture. The precipitated copolymerwas collected by filtration and dried at 65° C. in a vacuum oven. Thenthe polymer was dissolved in mesitylene to give 10 wt % solid copolymersolution. The polymer's molecular weight was determined by GPC methodsin THF using poly(styrene) as a standard: Mw=20,586; Mn=11,613. Theratio of HxNB/diPhNB in the polymer was determined by ¹H-NMR:HxNB/diPhNB=60/40. The composition of the copolymer was determined by1H-NMR to be 54/46 HxNB/diPhNB. The refractive indices of this polymerwere measured by prism coupling method and determined to be 1.5547 in TEmode and 1.5540 in TM mode at a wavelength of 633 nm. The driedcopolymer was dissolved in sufficient mesitylene to result in a 10 wt %copolymer solution.

Example P5 Synthesis of Hexylnorbornene/Diphenylmethyl NorbornenemethoxySilane Copolymer (P5)

HxNB, (8.94 g, 0.050 mol), diPhNB, (16.06 g, 0.050 mol), 1-hexene (5.0g, 0.060 mol) and toluene (142 g) were combined in a 500 mL serum bottleand heated to 80° C. in an oil bath to form a solution. To this solutionwere added Pd1446, (2.90E-3 g, 2.00E-6 mol), and DANFABA, (3.2E-3 g,4.01E-6 mol) each in the form of a concentrated solution ofdichloromethane. After the addition, the resulting mixture wasmaintained at 80° C. for 6 hours. The copolymer was precipitated byadding methanol drop wise into the vigorously stirred reaction mixture.The precipitated copolymer was collected by filtration and dried in anoven at 60° C. under vacuum. After drying, 19.3 g was obtained (77%).The molecular weight of the copolymer, determined by GPC in THF solvent(polystyrene standard) provided Mw=58,749 and Mn=18,177. The compositionof the copolymer was determined by ¹H-NMR to be 53/47 HxNB/diPhNB. Therefractive indices of this polymer were measured by prism couplingmethod and determined to be 1.5572 in TE mode and 1.5558 in TM mode at awavelength of 633 nm. The dried copolymer was dissolved in sufficientmesitylene to result in a 10 wt % copolymer solution.

Example P6 Synthesis of Butylnorbornene/Diphenylmethyl NorbornenemethoxySilane Copolymer (P6)

Butyl Norbornene (BuNB, CAS 22094-81-1) (2.62 g, 0.038 mol), diPhNB,(22.38 g, 0.057 mol), 1-hexene (8.83 g, 0.011 mol) and toluene (141.4 g)were combined in a 500 mL serum bottle and heated to 80° C. in an oilbath to form a solution. To this solution were injected Pd1446, (5.05E-3g, 3.49E-6 mol) and DANFABA (1.12E-2 g, 1.40E-5 mol) each in the form ofa concentrated solution in dichloromethane. After addition, theresulting mixture was maintained at 80° C. for 2 hours. The copolymerwas precipitated by adding methanol drop wise into the vigorouslystirred reaction mixture. The precipitated copolymer was collected byfiltration and dried in an oven at 60° C. under vacuum. After drying,7.5 g was obtained (30%). The molecular weight of the copolymer,determined by GPC in THF solvent (polystyrene standard) providedMw=32,665 and Mn=19,705. The composition of the copolymer was determinedby ¹H-NMR to be 28/72 HxNB/diPhNB. The refractive indices of thispolymer were measured by prism coupling method and determined to be1.5785 in TE mode and 1.5771 in TM mode at a wavelength of 633 nm. Thedried copolymer was dissolved in sufficient mesitylene to result in a 10wt % copolymer solution.

Example P8 Synthesis of Hexyl Norbornene Homopolymer (P8)

HxNB, (10.0 g, 0.056 mol), 1-hexene (4.71 g, 0.056 mol) and toluene(56.7 g) were combined in a 250 mL serum bottle and heated to 80° C. inan oil bath to form a solution. To this solution were added Pd1446,(4.10E-4 g, 2.80E-7 mol) and DANFABA, (2.20E-4 g, 2.80E-7 mol), each inthe form of a concentrated solution in dichloromethane. After addition,the resulting mixture was maintained at 80° C. for 40 minutes. Thehomopolymer was precipitated by adding methanol drop wise into thevigorously stirred reaction mixture. The precipitated copolymer wascollected by filtration and dried in an oven at 60° C. under vacuum.After drying, 5.8 g was obtained (58%). The molecular weight of thecopolymer, determined by GPC in THF solvent (polystyrene standard)provided Mw=121,541 and Mn=59,213. The refractive indices of thispolymer were measured by prism coupling method and determined to be1.5146 in TE mode and 1.5129 in TM mode at a wavelength of 633 nm. TheTg (based on thermomechanical analysis (TMA) measurement) of thispolymer was 208° C. The dried homopolymer was dissolved in sufficientmesitylene to result in a 10 wt % homopolymer solution.

Example P9 Synthesis of HexylNorbornene/Diphenylmethyl NorbornenemethoxySilane Copolymer (P9)

HxNB, (9.63 g, 0.054 mol), diPhNB, CAS 376634-34-3) (40.37 g, 0.126mol), 1-hexene (4.54 g, 0.054 mol) and toluene (333 g) were combined ina 500 mL serum bottle and heated to 80° C. in an oil bath to form asolution. To this solution were added Pd1446, (1.04E-2 g, 7.20E-6 mol)and N,N-dimethylanilinium tetrakis(pentafluorophenyl)borate (DANFABA)(2.30E-2 g, 2.88E-5 mol) each in the form of a concentrated solution ofdichloromethane. After addition, the resulting mixture was maintained at80° C. for 2 hours. The copolymer was precipitated by adding methanoldrop wise into the vigorously stirred reaction mixture. The precipitatedcopolymer was collected by filtration and dried in an oven at 60° C.under vacuum. After drying, 19.0 g was obtained (38%). The molecularweight of the copolymer, determined by GPC in THF solvent (polystyrenestandard) provided Mw=118,000 and Mn=60,000. The composition of thecopolymer was determined by ¹H-NMR to be 32/68 HxNB/diPhNB. Therefractive indices of this polymer were measured by prism couplingmethod and determined to be 1.5695 in TE mode and 1.5681 in TM mode at awavelength of 633 nm. The dried copolymer was dissolved in sufficientmesitylene to result in a 10 wt % copolymer solution.

Examples P11-P34

Examples P11 to P34 demonstrate the synthesis of norbornene-typepolymers useful as matrix polymers for materials in accordance withembodiments of the present invention.

Example P11 Synthesis of Diphenylmethyl Norbornenemethoxy Silanehomopolymer (P11)

diPhNB (30 g, 0.094 mol), 1-hexene (1.57 g, 0.019 mol) and toluene(170.0 g) were combined in a 250 mL serum bottle and heated to 80° C. inan oil bath to form a solution. To this solution were added[Pd(PCy3)2(O2CCH3)(NCCH3)]tetrakis(pentafluorophenyl)borate (Pd1446)(1.4E-2 g, 9.4E-6 mol) and N,N-dimethylaniliniumtetrakis(pentafluorophenyl)borate (DANFABA) (3.0E-2 g, 3.7E-5 mol), eachin the form of a concentrated dichloromethane solution. After addition,the resulting mixture was maintained at 80° C. for 4 hours. Thehomopolymer was precipitated by adding the solution drop wise into thevigorously stirred methanol. The precipitated homopolymer was collectedby filtration and dried in an oven at 60° C. under vacuum. After drying,15.0 g was obtained (Yield 50%). The molecular weight of the copolymerwas determined by GPC in THF solvent (polystyrene standard) to beMw=91,000 and Mn=44,000.

Example P12 Synthesis of Hexyl Norbornene/DiphenylmethylNorbornenemethoxy Silane Copolymer (P12)

HxNB (10.72 g, 0.06 mol), diPhNB (19.28 g, 0.06 mol), 1-hexene (3.5 g,0.04 mol) and toluene (170.0 g) were combined in a 250 mL serum bottleand heated to 80° C. in an oil bath to form a solution. To this solutionwere added [Pd(PCy3)2(O2CCH3)(NCCH3)]tetrakis(pentafluorophenyl)borate(Pd1446) (7.0E-3 g, 4.8E-6 mol) and N,N-dimethylaniliniumtetrakis(pentafluorophenyl)borate (DANFABA) (3.9E-3 g, 4.8E-6 mol), eachin the form of a concentrated dichloromethane solution. After addition,the resulting mixture was maintained at 80° C. for 3.5 hours. Thecopolymer was precipitated by adding the solution drop wise into thevigorously stirred methanol. The precipitated copolymer was collected byfiltration and dried in an oven at 60° C. under vacuum. After drying,18.6 g was obtained (Yield 62%). The molecular weight of the copolymerwas determined by GPC in THF solvent (polystyrene standard) to beMw=102,000 and Mn=38,000. The composition of the copolymer wasdetermined by 1H-NMR to be 54/46 HxNB/diPhNB. The dried copolymer wasdissolved in sufficient mesitylene to result in a 30 wt % copolymersolution.

Example P13 Synthesis of Butylnorbornene/DiphenylmethylNorbornenemethoxy Silane Copolymer (P13)

ButylNorbornene (BuNB, CAS 22094-81-1) (2.62 g, 0.038 mol), diPhNB,(22.38 g, 0.057 mol), 1-hexene (8.83 g, 0.011 mol) and toluene (141.4 g)were combined in a 500 mL serum bottle and heated to 80° C. in an oilbath to form a solution. To this solution were injected Pd1446, (5.05E-3g, 3.49E-6 mol) and DANFABA (1.12E-2 g, 1.40E-5 mol) each in the form ofa concentrated solution in dichloromethane. After addition, theresulting mixture was maintained at 80° C. for 2 hours. The copolymerwas precipitated by adding methanol drop wise into the vigorouslystirred reaction mixture. The precipitated copolymer was collected byfiltration and dried in an oven at 60° C. under vacuum. After drying,7.5 g was obtained (30%). The molecular weight of the copolymer,determined by GPC in THF solvent (polystyrene standard) providedMw=32,665 and Mn=19,705. The composition of the copolymer was determinedby 1H-NMR to be 28/72 HxNB/diPhNB. The refractive indices of thispolymer were measured by prism coupling method and determined to be1.5785 in 1E mode and 1.5771 in TM mode at a wavelength of 633 nm.

Example P14 Synthesis of HexylNorbornene/DiphenylmethylNorbornenemethoxy Silane Copolymer (P14)

HxNB (9.63 g, 0.054 mol), diPhNB (1.92 g, 0.006 mol), 1-hexene (5.04 g,0.060 mol) and toluene (56.7 g) were combined in a 250 mL serum bottleand heated to 80° C. in an oil bath to form a solution. To this solutionwere injected Pd1446 (4.30E-4 g, 3.00E-7 mol) and DANFABA (2.40E-4 g,3.00E-7 mol), each in the form of a concentrated solution indichloromethane. After addition, the resulting mixture was maintained at80° C. for 2 hours. The copolymer was precipitated by adding methanoldrop wise into the vigorously stirred reaction mixture. The precipitatedcopolymer was collected by filtration and dried in an oven at 60° C.under vacuum. After drying, 7.7 g was obtained (67%). The molecularweight of the copolymer was determined by GPC in THF solvent(polystyrene standard) to be Mw=82,000 and Mn=40,000. The composition ofthe copolymer was determined by 1H-NMR to be 89/11 HxNB/diPhNB. Therefractive indices of this polymer were measured by prism couplingmethod and determined to be 1.5238 in TE mode and 1.5225 in TM mode at awavelength of 633 nm. The dried copolymer was dissolved in sufficientmesitylene to result in a 30 wt % copolymer solution.

Example P15 Synthesis of Diphenylmethyl Norbornenemethoxy SilaneHomopolymer (P15)

diPhNB (30.00 g, 0.094 mol), 1-hexene (2.36 g, 0.028 mol) and toluene(170.0 g) were combined in a 500 mL serum bottle and heated to 80° C. inan oil bath to form a solution. To this solution were injected Pd1446(0.0135 g, 9.36E-6 mol) and DANFABA (0.030 g, 3,74E-5 mol), each in theform of a concentrated solution in dichloromethane. After addition, theresulting mixture was maintained at 80° C. for 4 hours. The homopolymerwas precipitated by adding methanol drop wise into the vigorouslystirred reaction mixture. The precipitated homopolymer was collected byfiltration and dried in an oven at 60° C. under vacuum. After drying,25.18 g was obtained (21%). The molecular weight of the copolymer wasdetermined by GPC in THF solvent (polystyrene standard) to be Mw=54,000and Mn=29,000. The composition of the copolymer was determined by 1H-NMRto be diPhNB homopolymer. The refractive indices of this polymer weremeasured by prism coupling method and determined to be 1.5926 in TE modeand 1.5910 in TM mode at a wavelength of 633 nm. The dried homopolymerwas dissolved in sufficient toluene to result in a 30 wt % homopolymersolution.

Example P16 Synthesis of Butyl Norbornene/Phenylethyl NorborneneCopolymer (P16)

BuNB (4.78 g, 0.032 mol), PENB (25.22 g, 0.127 mol), 1-hexene (13.36 g,0.16 mol) and toluene (170.0 g) were combined in a 500 mL serum bottleand heated to 80° C. in an oil bath to form a solution. To this solutionwere injected Pd1446 (0.0092 g, 6.36E-06 mol) and DANFABA (0.020 g,2.54E-5 mol), each in the form of a concentrated solution indichloromethane. After addition, the resulting mixture was maintained at80° C. for 50 minutes. The copolymer was precipitated by adding methanoldrop wise into the vigorously stirred reaction mixture. The precipitatedcopolymer was collected by filtration and dried in an oven at 60° C.under vacuum. After drying, 23.60 g was obtained (79%). The molecularweight of the copolymer was determined by GPC in THF solvent(polystyrene standard) to be Mw=73,000 and Mn=28,000. The composition ofthe copolymer was determined by 1H-NMR to be (15/85) BuNB/PENBcopolymer. The refractive indices of this polymer were measured by prismcoupling method and determined to be 1.5684 in TE mode and 1.5657 in TMmode at a wavelength of 633 nm. The dried copolymer was dissolved insufficient toluene to result in a 30 wt % copolymer solution.

Example P17 Synthesis of Hexyl Norbornene/Phenylethyl NorborneneCopolymer (P17)

HxNB (6.00 g, 0.034 mol), PENB (26.69 g, 0.135 mol), 1-hexene (11.31 g,0.135 mol) and toluene (185.35 g) were combined in a 500 mL serum bottleand heated to 80° C. in an oil bath to form a solution. To this solutionwere injected Pd1446 (0.0097 g, 6.73E-06 mol) and DANFABA (0.022 g,2.69E-5 mol), each in the form of a concentrated solution indichloromethane. After addition, the resulting mixture was maintained at80° C. for 50 minutes. The copolymer was precipitated by adding methanoldrop wise into the vigorously stirred reaction mixture. The precipitatedcopolymer was collected by filtration and dried in an oven at 60° C.under vacuum. After drying, 22.21 g was obtained (68%). The molecularweight of the copolymer was determined by GPC in THF solvent(polystyrene standard) to be Mw=95,000 and Mn=26,000. The composition ofthe copolymer was determined by 1H-NMR to be (17/83) HxNB/PENBcopolymer. The refractive indices of this polymer were measured by prismcoupling method and determined to be 1.5477 in TE mode and 1.5454 in TMmode at a wavelength of 633 nm. The dried copolymer was dissolved insufficient toluene to result in a 30 wt % copolymer solution.

Example P18 Synthesis of Decyl Norbornene/Phenylethyl NorborneneCopolymer (P18)

Decyl Norbornene (DeNB, CAS 22094-85-5) (6.84 g, 0.029 mol), PENB (23.16g, 0.117 mol), 1-hexene (12.26 g, 0.146 mol) and toluene (170.0 g) werecombined in a 500 mL serum bottle and heated to 80° C. in an oil bath toform a solution. To this solution were injected Pd1446 (0.0084 g,5.84E-06 mol) and DANFABA (0.019 g, 2.33E-5 mol), each in the form of aconcentrated solution in dichloromethane. After addition, the resultingmixture was maintained at 80° C. for 50 minutes. The copolymer wasprecipitated by adding methanol drop wise into the vigorously stirredreaction mixture. The precipitated copolymer was collected by filtrationand dried in an oven at 60° C. under vacuum. After drying, 19.74 g wasobtained (66%). The molecular weight of the copolymer was determined byGPC in THF solvent (polystyrene standard) to be Mw=78,000 and Mn=36,000.The composition of the copolymer was determined by 1H-NMR to be (19/81)DeNB/PENB copolymer. The refractive indices of this polymer weremeasured by prism coupling method and determined to be 1.5640 in TE modeand 1.5622 in TM mode at a wavelength of 633 nm. The dried copolymer wasdissolved in sufficient toluene to result in a 30 wt % copolymersolution.

Example P19 Synthesis of Benzyl Norbornene Homopolymer (P19)

Benzyl Norbornene (BzNB, CAS 265989-73-9) (30.00 g, 0.163 mol), triethylsilane (0.227 g, 1.95E-03 mol), ethanol (0.360 g, 7.81E-03 mol) andtoluene (170.0 g) were combined in a 500 mL serum bottle and heated to80° C. in an oil bath to form a solution. To this solution were injectedPd1446 (0.0188 g, 1.30E-05 mol) and DANFABA (0.042 g, 5.21E-5 mol), eachin the form of a concentrated solution in dichloromethane. Afteraddition, the resulting mixture was maintained at 80° C. for 1.5 hours.The homopolymer was precipitated by adding methanol drop wise into thevigorously stirred reaction mixture. The precipitated homopolymer wascollected by filtration and dried in an oven at 60° C. under vacuum.After drying, 15.07 g was obtained (50%). The molecular weight of thehomopolymer was determined by GPC in THF solvent (polystyrene standard)to be Mw=46,000 and Mn=28,000. The composition of the homopolymer wasdetermined by 1H-NMR to be BzNB homopolymer. The refractive indices ofthis polymer were measured by prism coupling method and determined to be1.5778 in TE mode and 1.5757 in TM mode at a wavelength of 633 nm. Thedried homopolymer was dissolved in sufficient toluene to result in a 30wt % homopolymer solution

Example P20 Synthesis of Hexyl Norbornene/Benzyl Norbornene Copolymer(P20)

HxNB (8.79 g, 0.049 mol), BzNB (21.21 g, 0.115 mol), triethyl silane(0.23 g, 1.97E-03 mol), ethanol (0.36 g, 7.89E-03 mol) and toluene(170.0 g) were combined in a 500 mL serum bottle and heated to 80° C. inan oil bath to form a solution. To this solution were injected Pd1446(0.019 g, 1.32E-05 mol) and DANFABA (0.042 g, 5.26E-5 mol), each in theform of a concentrated solution in dichloromethane. After addition, theresulting mixture was maintained at 80° C. for 1.5 hours. The copolymerwas precipitated by adding methanol drop wise into the vigorouslystirred reaction mixture. The precipitated copolymer was collected byfiltration and dried in an oven at 60° C. under vacuum. After drying,18.59 g was obtained (62%). The molecular weight of the copolymer wasdetermined by GPC in THE solvent (polystyrene standard) to be Mw=52,000and Mn=30,000. The composition of the copolymer was determined by 1H-NMRto be (35/65) HxNB/BzNB copolymer. The refractive indices of thispolymer were measured by prism coupling method and determined to be1.5597 in TE mode and 1.5579 in TM mode at a wavelength of 633 nm. Thedried copolymer was dissolved in sufficient toluene to result in a 30 wt% copolymer solution.

Example P21 Synthesis of Decyl Norbornene/Benzyl Norbornene Copolymer(P21)

DeNB (6.84 g, 0.029 mol), BzNB (21.56 g, 0.117 mol), 1-hexene (12.26 g,0.146 mol) and toluene (170.0 g) were combined in a 500 mL serum bottleand heated to 80° C. in an oil bath to form a solution. To this solutionwere injected Pd1446 (0.0084 g, 5.84E-06 mol) and DANFABA (0.019 g,2.33E-5 mol), each in the form of a concentrated solution indichloromethane. After addition, the resulting mixture was maintained at80° C. for 1.5 hours. The copolymer was precipitated by adding methanoldrop wise into the vigorously stiffed reaction mixture. The precipitatedcopolymer was collected by filtration and dried in an oven at 60° C.under vacuum. After drying, 20.73 g was obtained (73%). The molecularweight of the copolymer was determined by GPC in THF solvent(polystyrene standard) to be Mw=64,000 and Mn=31,000. The composition ofthe copolymer was determined by 1H-NMR to be (27/73) DeNB/BzNBcopolymer. The refractive indices of this polymer were measured by prismcoupling method and determined to be 1.5680 in TE mode and 1.5662 in TMmode at a wavelength of 633 nm. The dried copolymer was dissolved insufficient toluene to result in a 30 wt % copolymer solution.

Example P22 Synthesis of Butyl Norbornene/Methyl Glycidyl EtherNorbornene Copolymer (P22)

BuNB (10.52 g, 0.07 mol), Methyl Glycidyl Ether Norbornene (AGENB, CAS3188-75-8) (5.41 g, 0.03 mol), toluene (58.0 g) were added to a serumbottle in the drybox. The solution was stirred at 80° C. in an oil bath.To this solution were added a toluene solution (5 g) of(η⁶-toluene)Ni(C₆F₅)₂ (0.69 g, 0.0014 mol). After the addition, theresulting mixture was maintained at room temperature for 4 hours. Atoluene solution (87.0 g) was added to the reaction solution. Thecopolymer was precipitated by adding methanol drop wise into thevigorously stirred reaction mixture. The precipitated copolymer wascollected by filtration and dried in an oven at 60° C. under vacuum.After drying, 12.74 g was obtained (80%). The molecular weight of thecopolymer was determined by GPC in THF solvent (polystyrene standard) tobe Mw=75,000 and Mn=30,000. The composition of the copolymer wasdetermined by 1H-NMR to be (78/22) BuNB/AGENB copolymer. The refractiveindices of this polymer were measured by prism coupling method anddetermined to be 1.5162 in TE mode and 1.5157 in TM mode at a wavelengthof 633 nm. The dried copolymer was dissolved in sufficient toluene toresult in a 30 wt % copolymer solution.

Example P23 Synthesis of Hexyl Norbornene/Methyl Glycidyl EtherNorbornene Copolymer (P23)

HxNB (12.48 g, 0.07 mol), AGENB (5.41 g, 0.03 mol), toluene (58.0 g)were added to a serum bottle in the drybox. The solution was stirred at80° C. in an oil bath. To this solution were added a toluene solution (5g) of (η⁶-toluene)Ni(C₆F₅)₂ (0.69 g, 0.0014 mol). After the addition,the resulting mixture was maintained at room temperature for 4 hours. Atoluene solution (87.0 g) was added to the reaction solution. Thecopolymer was precipitated by adding methanol drop wise into thevigorously stirred reaction mixture. The precipitated copolymer wascollected by filtration and dried in an oven at 60° C. under vacuum.After drying, 13.78 g was obtained (77%). The molecular weight of thecopolymer was determined by GPC in THF solvent (polystyrene standard) tobe Mw=78,000 and Mn=33,000. The composition of the copolymer wasdetermined by 1H-NMR to be (79/21) HxNB/AGENB copolymer. The refractiveindices of this polymer were measured by prism coupling method anddetermined to be 1.5159 in TE mode and 1.5153 in TM mode at a wavelengthof 633 nm. The dried copolymer was dissolved in sufficient toluene toresult in a 30 wt % copolymer solution.

Example P24 Synthesis of Decyl Norbornene/Methyl Glycidyl EtherNorbornene Copolymer (P24)

DeNB (16.4 g, 0.07 mol), AGENB (5.41 g, 0.03 mol), toluene (58.0 g) wereadded to a serum bottle in the drybox. The solution was stirred at 80°C. in an oil bath. To this solution were added a toluene solution (5 g)of (η⁶-toluene)Ni(C₆F₅)₂ (0.69 g, 0.0014 mol). After the addition, theresulting mixture was maintained at room temperature for 4 hours. Atoluene solution (87.0 g) was added to the reaction solution. Thecopolymer was precipitated by adding methanol drop wise into thevigorously stirred reaction mixture. The precipitated copolymer wascollected by filtration and dried in an oven at 60° C. under vacuum.After drying, 17.00 g was obtained (87%). The molecular weight of thecopolymer was determined by GPC in THF solvent (polystyrene standard) tobe Mw=75,000 and Mn=30,000. The composition of the copolymer wasdetermined by 1H-NMR to be (77/23) DeNB/AGENB copolymer. The refractiveindices of this polymer were measured by prism coupling method anddetermined to be 1.5153 in TE mode and 1.5151 in TM mode at a wavelengthof 633 nm. The dried copolymer was dissolved in sufficient toluene toresult in a 30 wt % copolymer solution.

Example P25 Synthesis of ButylNorbornene/Norbornenylethyltrimethoxysilane Copolymer (P25)

BuNB (25.44 g, 0.169 mol), Norbornenylethyltrimethoxysilane (TMSENB, CAS68245-19-2) (4.56 g, 0.019 mol), triethyl silane (0.11 g, 9.41E-04 mol),ethanol (0.10 g, 2.26E-03 mol) and toluene (170.0 g) were combined in a300 mL serum bottle and heated to 80° C. in an oil bath to form asolution. To this solution were injected Pd1446 (0.022 g, 1.50E-05 mol)and DANFABA (0.036 g, 4.51E-5 mol), each in the form of a concentratedsolution in dichloromethane. After addition, the resulting mixture wasmaintained at 80° C. for 4 hours. The copolymer was precipitated byadding methanol drop wise into the vigorously stirred reaction mixture.The precipitated copolymer was collected by filtration and dried in anoven at 60° C. under vacuum. After drying, 22.60 g was obtained (69%).The molecular weight of the copolymer was determined by GPC in THFsolvent (polystyrene standard) to be Mw=20,000 and Mn=13,000. Thecomposition of the copolymer was determined by 1H-NMR to be (91/9)BuNB/TMSENB copolymer. The refractive indices of this polymer weremeasured by prism coupling method and determined to be 1.5106 in TE modeand 1.5105 in TM mode at a wavelength of 633 nm. The dried copolymer wasdissolved in sufficient toluene to result in a 30 wt % copolymersolution.

Example P26 Synthesis of HexylNorbornene/Norbornenylethyltrimethoxysilane Copolymer (P26)

HxNB (13.03 g, 0.073 mol), TMSENB (1.97 g, 0.0081 mol), triethyl silane(0.019 g, 1.62E-04 mol), ethanol (0.030 g, 6.50E-04 mol) and toluene(85.0 g) were combined in a 300 mL serum bottle and heated to 80° C. inan oil bath to form a solution. To this solution were injected[Pd(P(iPr)₃)₂(OCOCH₃)(NCCH₃)]tetrakis(pentafluorophenyl)borate (Pd1206)(0.0078 g, 6.50E-06 mol) in the form of a concentrated solution indichloromethane. After addition, the resulting mixture was maintained at80° C. for 4 hours. The copolymer was precipitated by adding methanoldrop wise into the vigorously stirred reaction mixture. The precipitatedcopolymer was collected by filtration and dried in an oven at 60° C.under vacuum. After drying, 3.30 g was obtained (22%). The molecularweight of the copolymer was determined by GPC in THF solvent(polystyrene standard) to be Mw=53,000 and Mn=33,000. The composition ofthe copolymer was determined by 1H-NMR to be (93/7) HxNB/TMSENBcopolymer. The refractive indices of this polymer were measured by prismcoupling method and determined to be 1.5126 in TE mode and 1.5114 in TMmode at a wavelength of 633 nm. The dried copolymer was dissolved insufficient toluene to result in a 30 wt % copolymer solution.

Example P27 Synthesis of DecylNorbornene/Norbornenylethyltrimethoxysilane Copolymer (P27)

DeNB (22.31 g, 0.095 mol), TMSENB (7.69 g, 0.032 mol), triethyl silane(0.44 g, 3.81E-04 mol), ethanol (0.70 g, 1.52E-03 mol) and toluene(170.0 g) were combined in a 500 mL serum bottle and heated to 80° C. inan oil bath to form a solution. To this solution were injected Pd1446(0.015 g, 1.02E-05 mol) and DANFABA (0.024 g, 3.05E-5 mol), each in theform of a concentrated solution in dichloromethane. After addition, theresulting mixture was maintained at 80° C. for 4 hours. The copolymerwas precipitated by adding methanol drop wise into the vigorouslystirred reaction mixture. The precipitated copolymer was collected byfiltration and dried in an oven at 60° C. under vacuum. After drying,12.2 g was obtained (40.7%). The molecular weight of the copolymer wasdetermined by GPC in THF solvent (polystyrene standard) to be Mw=34,000and Mn=24,000. The composition of the copolymer was determined by 1H-NMRto be (77/23) DeNB/TMSENB copolymer. The refractive indices of thispolymer were measured by prism coupling method and determined to be1.5063 in TE mode and 1.5062 in TM mode at a wavelength of 633 nm. Thedried copolymer was dissolved in sufficient toluene to result in a 30 wt% copolymer solution.

Example P28 Synthesis of Butyl Norbornene/Triethoxysilyl NorborneneCopolymer (P28)

BuNB (25.22 g, 0.168 mol), Triethoxysilyl Norbornene (TESNB, CAS18401-43-9) (4.78 g, 0.019 mol), triethyl silane (0.011 g, 9.32E-05mol), ethanol (0.10 g, 224E-03 mol) and toluene (170.0 g) were combinedin a 500 mL serum bottle and heated to 80° C. in an oil bath to form asolution. To this solution were injected Pdl 206 (0.018 g, 1.49E-05 mol)in the form of a concentrated solution in dichloromethane. Afteraddition, the resulting mixture was maintained at 80° C. for 9 hours.The copolymer was precipitated by adding methanol drop wise into thevigorously stirred reaction mixture. The precipitated copolymer wascollected by filtration and dried in an oven at 60° C. under vacuum.After drying, 20.58 g was obtained (69%). The molecular weight of thecopolymer was determined by GPC in THF solvent (polystyrene standard) tobe Mw=238,000 and Mn=96,000. The composition of the copolymer wasdetermined by 1H-NMR to be (85/15) BuNB/TESNB copolymer. The refractiveindices of this polymer were measured by prism coupling method anddetermined to be 1.5061 in TE mode and 1.5041 in TM mode at a wavelengthof 633 nm. The Tg (based on thermomechanical analysis (TMA) measurement)of this polymer was 276° C. The dried copolymer was dissolved insufficient toluene to result in a 30 wt % copolymer solution.

Example P29 Synthesis of Hexyl Norbornene/Triethoxysilyl NorborneneCopolymer (P29)

HxNB (20.33 g, 0.114 mol), TESNB (3.26 g, 0.013 mol), triethyl silane(0.030 g, 2.54E-03 mol), ethanol (0.07 g, 1.52E-03 mol) and toluene(170.0 g) were combined in a 500 mL serum bottle and heated to 80° C. inan oil bath to form a solution. To this solution were injected Pd1446(0.015 g, 1.01E-05 mol) in the form of a concentrated solution indichloromethane. After addition, the resulting mixture was maintained at80° C. for 9 hours. The copolymer was precipitated by adding methanoldrop wise into the vigorously stirred reaction mixture. The precipitatedcopolymer was collected by filtration and dried in an oven at 60° C.under vacuum. After drying, 7.31 g was obtained (31%). The molecularweight of the copolymer was detemfined by GPC in THF solvent(polystyrene standard) to be Mw=234,000 and Mn=110,000. The compositionof the copolymer was determined by 1H-NMR to be (83/17) HxNB/TESNBcopolymer. The refractive indices of this polymer were measured by prismcoupling method and determined to be 1.5053 in TE mode and 1.5042 in TMmode at a wavelength of 633 nm. The dried copolymer was dissolved insufficient toluene to result in a 30 wt % copolymer solution.

Example P30 Synthesis of Decyl Norbornene/Triethoxysilyl NorborneneCopolymer (P30)

DeNB (26.77 g, 0.114 mol), TESNB (3.26 g, 0.013 mol), triethyl silane(0.030 g, 2.54E-03 mol), ethanol (0.07 g, 1.52E-03 mol) and toluene(170.0 g) were combined in a 500 mL serum bottle and heated to 80° C. inan oil bath to form a solution. To this solution were injected Pd1446(0.015 g, 1.01E-05 mol) in the form of a concentrated solution indichloromethane. After addition, the resulting mixture was maintained at80° C. for 9 hours. The copolymer was precipitated by adding methanoldrop wise into the vigorously stirred reaction mixture. The precipitatedcopolymer was collected by filtration and dried in an oven at 60° C.under vacuum. After drying, 18.01 g was obtained (60%). The molecularweight of the copolymer was determined by GPC in THF solvent(polystyrene standard) to be Mw=283,000 and Mn=118,000. The compositionof the copolymer was determined by 1H-NMR to be (84/16) DeNB/TESNBcopolymer. The refractive indices of this polymer were measured by prismcoupling method and determined to be 1.5034 in 1 mode and 1.5018 in TMmode at a wavelength of 633 nm. The dried copolymer was dissolved insufficient toluene to result in a 30 wt % copolymer solution.

Example P31 Synthesis of Butyl Norbornene/Trimethoxysilyl NorborneneCopolymer (P31)

BuNB (10.97 g, 0.073 mol), TrimethoxysilylNorbornene (TMSNB, CAS7538-46-7) (12.95 g, 0.073 mol), triethyl silane (0.34 g, 2.91E-04 mol),ethanol (0.80 g, 1.75E-03 mol) and toluene (170.0 g) were combined in a500 mL serum bottle and heated to 80° C. in an oil bath to form asolution. To this solution were injected Pd1446 (0.017 g, 1.16E-05 mol)and DANFABA (0.028 g, 3.49E-5 mol), each in the form of a concentratedsolution in dichloromethane. After addition, the resulting mixture wasmaintained at 80° C. for 4 hours. The copolymer was precipitated byadding methanol drop wise into the vigorously stirred reaction mixture.The precipitated copolymer was collected by filtration and dried in anoven at 60° C. under vacuum. After drying, 15.5 g was obtained (65%).The molecular weight of the copolymer was determined by GPC in THFsolvent (polystyrene standard) to be Mw=48,000 and Mn=27,000. Thecomposition of the copolymer was determined by 1H-NMR to be (47/53)BuNB/TMSNB copolymer. The refractive indices of this polymer weremeasured by prism coupling method and determined to be 1.5093 in TE modeand 1.5089 in TM mode at a wavelength of 633 nm. The dried copolymer wasdissolved in sufficient toluene to result in a 30 wt % copolymersolution.

Example P32 Synthesis of Hexyl Norbornene/Trimethoxysilyl NorborneneCopolymer (P32)

HxNB (13.02 g, 0.073 mol), TMSNB (12.95 g, 0.073 mol), triethyl silane(0.34 g, 2.91E-04 mol), ethanol (0.80 g, 1.75E-03 mol) and toluene(170.0 g) were combined in a 500 mL serum bottle and heated to 80° C. inan oil bath to form a solution. To this solution were injected Pd1446(0.017 g, 1.16E-05 mol) and DANFABA (0.028 g, 3.49E-5 mol), each in theform of a concentrated solution in dichloromethane. After addition, theresulting mixture was maintained at 80° C. for 4 hours. The copolymerwas precipitated by adding methanol drop wise into the vigorouslystirred reaction mixture. The precipitated copolymer was collected byfiltration and dried in an oven at 60° C. under vacuum. After drying,17.7 g was obtained (68%). The molecular weight of the copolymer wasdetermined by GPC in THF solvent (polystyrene standard) to be Mw=55,000and Mn=27,000. The composition of the copolymer was determined by 1H-NMRto be (46/54) HxNB/TMSNB copolymer. The refractive indices of thispolymer were measured by prism coupling method and determined to be1.5081 in TE mode and 1.5078 in TM mode at a wavelength of 633 nm. Thedried copolymer was dissolved in sufficient toluene to result in a 30 wt% copolymer solution.

Example P33 Synthesis of Decyl Norbornene/Trimethoxysilyl NorborneneCopolymer (P33)

DeNB (17.05 g, 0.073 mol), TMSNB (12.95 g, 0.073 mol), triethyl silane(0.34 g, 2.91E-04 mol), ethanol (0.80 g, 1.75E-03 mol) and toluene(170.0 g) were combined in a 500 mL serum bottle and heated to 80° C. inan oil bath to form a solution. To this solution were injected Pd1446(0.017 g, 1.16E-05 mol) and DANFABA (0.028 g, 3.49E-5 mol), each in theform of a concentrated solution in dichloromethane. After addition, theresulting mixture was maintained at 80° C. for 4 hours. The copolymerwas precipitated by adding methanol drop wise into the vigorouslystirred reaction mixture. The precipitated copolymer was collected byfiltration and dried in an oven at 60° C. under vacuum. After drying,21.1 g was obtained (70%). The molecular weight of the copolymer wasdetermined by GPC in THF solvent (polystyrene standard) to be Mw=82,000and Mn=31,000. The composition of the copolymer was determined by 1H-NMRto be (46/54) DeNB/TMSNB copolymer. The refractive indices of thispolymer were measured by prism coupling method and determined to be1.5029 in TE mode and 1.5016 in TM mode at a wavelength of 633 nm. Thedried copolymer was dissolved in sufficient toluene to result in a 30 wt% copolymer solution.

Example P34 Synthesis of Hexyl Norbornene/DiphenylmethylNorbornenemethoxy Silane/Norbornenylethyltrimethoxysilane Terpolymer(P34)

HxNB (5.94 g, 0.033 mol), diPhNB (21.36 g, 0.067 mol), TMSENB (2.69 g,0.011 mol), 1-Hexene (3.73 g, 0.044 mol) and toluene (170.0 g) werecombined in a 500 mL serum bottle and heated to 80° C. in an oil bath toform a solution. To this solution were injected Pd1446 (0.0064 g,4.44E-06 mol) and DANFABA (0.0036 g, 4.44E-6 mol), each in the form of aconcentrated solution in dichloromethane. After addition, the resultingmixture was maintained at 80° C. for 3.5 hours. The copolymer wasprecipitated by adding methanol drop wise into the vigorously stirredreaction mixture. The precipitated copolymer was collected by filtrationand dried in an oven at 60° C. under vacuum. After drying, 10.26 g wasobtained (34%). The molecular weight of the copolymer was determined byGPC in THF solvent (polystyrene standard) to be Mw=105,000 andMn=54,000. The composition of the copolymer was determined by 1H-NMR tobe (38/54/8) HxNB//diPhNB/TMSENB copolymer. The refractive indices ofthis polymer were measured by prism coupling method and determined to be1.5586 in TE mode and 1.5572 in TM mode at a wavelength of 633 nm. Thedried terpolymer was dissolved in sufficient toluene to result in a 30wt % terpolymer solution.

Table 1 provides a summary of each exemplary polymer discussed above.

TABLE 1 P1 Hx/diPh (50/50) Mw = 16,196 P2 Hx/PE (30/70) Mw = 127,332 P3Hx/diPh (50/50) Mw = 86,186 P4 Hx/diPh (50/50) Mw = 20,586 P5 Hx/diPh(50/50) Mw = 58,749 P6 Bu/diPh (30/70) Mw = 32,665 P8 Hx Mw = 121,541 P9Hx/diPh (30/70) Mw = 82,000 P11 diPh Mw = 91,000 P12 Hx/diPh (50/50) Mw= 102,000 P13 Bu/diPh (40/60) Mw = 32,665 P14 Hx/diPh (90/10) Mw =82,000 P15 diPh homo Mw = 54,000 P16 Bu/PE (20/80) Mw = 73,000 P17 Hx/PE(20/80) Mw = 95,000 P18 De/PE (20/80) Mw = 78,000 P19 Bz homo Mw =46,000 P20 Hx/Bz (30/70) Mw = 52,000 P21 De/Bz (20/80) Mw = 64,000 P22Bu/AGE (70/30) Mw = 75,000 P23 Hx/AGE (70/30) Mw = 78,000 P24 De/AGE(70/30) Mw = 75,000 P25 Bu/TMSE (90/10) Mw = 20,000 P26 Hx/TMSE (90/10)Mw = 53.000 P27 De/TMSE (75/25) Mw = 34,000 P28 Bu/TES (90/10) Mw =238,000 P29 Hx/TES (90/10) Mw = 234,000 P30 De/TES (90/10) Mw = 283,000P31 Bu/TMS (50/50) Mw = 48,000 P32 Hx/TMS (50/50) Mw = 55,000 P33 De/TMS(50/50) Mw = 82,000 P34 Terpolymer (Hx 30/diPh 60/TMSE 10) Mw = 105,000Varnishes

Examples V1-V13, V38-V48 and V63-V66

Examples V1 to V13, V38 to V48 and V63 to V66 demonstrate theformulation of varnish solutions encompassing matrix polymers,norbornene-type monomers, a procatalyst, an acid generator, optionalantioxidants and solvents in accordance with embodiments of the presentinvention. It will be noted that as each of the varnish solutionsexemplified below incorporates a photo sensitive material, suchsolutions were formulated under yellow light.

Example V1

HxNB (42.03 g, 0.24 mol) and bis-Norbornenemethoxy dimethylsilane (SiX,CAS 376609-87-9) (7.97 g, 0.026 mol) were weighed out into a glass vial.To this solution of monomers were added two antioxidants, Ciba® IRGANOX®1076 (0.5 g) and Ciba® IRGAFOS® 168 (0.125 g) (both available from CibaSpecialty Chemicals Corporation, Tarrytown, N.Y.) to form amonomer-antioxidant solution. To 30.0 g of the above prepared P1copolymer solution, were added 3.0 g of the monomer-antioxidantsolution, Pd(PCy₃)₂(OAc)₂ (Pd785) (4.94E-4 g, 6.29E-7 mol in 0.1 mL ofmethylene chloride), RHODORSIL® PHOTOINITIATOR 2074 (CAS 178233-72-2,available from Rhodia Inc, Cranbury, N.J.) (2.55E-3 g, 2.51E-6 mol in0.1 mL of methylene chloride) to form the varnish solution. The varnishsolution was filtered through a 0.2-micron pore filter prior to use.

Example V2

SiX (5 g, 0.0164 mol) was weighed out in a glass vial. To the SiX wereadded Irganox 1076 (0.05 g) and Irgafos 168 (0.013 g) to form an SiXsolution. Varnish solution V2 was prepared by mixing SiX solution (3 g),Pd-785 stock solution (3.10E-4 g, 3.94E-7 mol in 0.1 mL of methylenechloride), Rhodorsil 2074 stock solution (1.60E-3 g, 1.58E-6 mol in 0.1mL of methylene chloride) and P2 copolymer solution (30 g, solid 3 g).The ratio of copolymer/monomers was 1/1 by weight and the ratio ofmonomers/Pd catalyst/Photo acid generator (PAG) was 25K/1/4 by mol. Thevarnish solution was filtered through a 0.2-micron pore filter.

Example V3

HxNB (42.03 g, 0.24 mol) and SiX (7.97 g, 0.026 mol) were weighed outinto a glass vial. To this solution of monomers were added twoantioxidants, Ciba® IRGANOX 1076 (0.5 g) and Ciba® IRGAFOS 168 (0.125 g)to form a monomer-antioxidant solution. To 30.0 g of copolymer solution(10 g of P3+20 g of P4), were added 3.0 g of the monomer-antioxidantsolution, Pd785 (4.93E-4 g, 6.28E-7 mol in 0.1 mL of methylenechloride), RHODORSIL® PHOTOINITIATOR 2074 (2.55E-3 g, 2.51 E-6 mol in0.1 mL of methylene chloride) to form the varnish solution V3. Thissolution was filtered through a 0.2-micron pore filter prior to use.

Example V4

Varnish Solution V4 was prepared as above for V3, except that the 30.0 gof copolymer solution was 15 g of P3 and 15 g of P4 to form the varnishsolution V4. This solution was filtered with 0.2-micron pore filterprior to use.

Example V5

Varnish Solution V5 was prepared as above for V3, except that the 30.0 gof copolymer solution was 20 g of P3 and 10 g of P4 to form the varnishsolution V5. This solution was filtered through a 0.2-micron pore filterprior to use.

Example V6

Varnish Solution V6 was prepared as above for V3, except that the 30.0 gof copolymer solution was 30 g of P3 to form the varnish solution V6.This solution was filtered through a 0.2-micron pore filter prior touse.

Example V7

HxNB (40.33 g, 0.23 mol) and Norbornenylethyltriemethoxysilane (TMSENB,CAS 68245-19-2) (9.67 g, 0.039 mol) were weighed out into a glass vial.To this solution of monomers were added two antioxidants, Ciba® IRGANOX1076 (0.5 g) and Ciba® IRGAFOS 168 (0.125 g) to form amonomer-antioxidant solution. To 30.0 g of the above copolymer solution(15 g of P3+15 g of P4) depicted in Table 1, were added 3.0 g of themonomer-antioxidant solution, Pd785 (5.02E-4 g, 6.39E-7 mol in 0.1 mL ofmethylene chloride), RHODORSIL® PHOTOINITIATOR 2074 (2.59E-3 g, 2.55E-6mol in 0.1 mL of methylene chloride) to form the varnish solution V7.This solution was filtered through a 0.2-micron pore filter prior touse.

Example V8

HxNB (42.03 g, 0.24 mol) and SiX, (7.97 g, 0.026 mol) were weighed outinto a glass vial. To this solution of monomers were added twoantioxidants, Ciba® IRGANOX 1076 (0.5 g) and Ciba® IRGAFOS 168 (0.125 g)to form a monomer-antioxidant solution. To 18.3 g of the above preparedcopolymer P5 solution, were added 3.06 g of the monomer-antioxidantsolution, Pd785 (3.85E-4 g, 4.91E-7 mol in 0.1 mL of methylenechloride), RHODORSIL® PHOTOINITIATOR 2074 (1.99E-3 g, 1.96E-6 mol in 0.1mL of methylene chloride) and 1.30 g of mesitylene and to form thevarnish solution.

Example V9

HxNB (42.03 g, 0.24 mol) and SiX, (7.97 g, 0.026 mol) were weighed outinto a glass vial. To this solution of monomers were added twoantioxidants, Ciba® IRGANOX 1076 (0.5 g) and Ciba® IRGAFOS 168 (0.125 g)to form a monomer-antioxidant solution. To 9.15 g of the above preparedcopolymer P6 solution, were added 1.53 g of the monomer-antioxidantsolution, Pd785 (2.52E-4 g, 3.21E-7 mol in 0.1 mL of methylenechloride), RHODORSIL® PHOTOINITIATOR 2074 (1.30E-3 g, 1.28E-6 mol in 0.1mL of methylene chloride) and 0.645 g of mesitylene to form the varnishsolution.

Example V10

HxNB (42.03 g, 0.24 mol) and SiX, (7.97 g, 0.026 mol) were weighed outinto a glass vial. To this solution of monomers were added twoantioxidants, Ciba® IRGANOX 1076 (0.5 g) and Ciba® IRGAFOS 168 (0.125 g)to form a monomer-antioxidant solution. To 20 g of the above preparedcopolymer P3 solution, were added 2.4 g of the monomer-antioxidantsolution, Pd785 (3.95E-4 g, 5.03E-7 mol in 0.1 mL of methylenechloride), RHODORSIL® PHOTOINITIATOR 2074 (2.55E-3 g, 2.51E-6 mol in 0.1mL of methylene chloride) and 2.5 g of toluene and to form the varnishsolution. The varnish solution was filtered through a 0.2-micron porefilter prior to use.

Example V11

HxNB (42.03 g, 0.24 mol) and SiX, (7.97 g, 0.026 mol) were weighed outinto a glass vial. To this solution of monomers were added twoantioxidants, Ciba® IRGANOX 1076 (0.5 g) and Ciba® IRGAFOS 168 (0.125 g)to form a monomer-antioxidant solution. To 20 g of the above preparedhomopolymer P8 solution, were added 2.4 g of the monomer-antioxidantsolution, Pd785 (3.95E-4 g, 5.03E-7 mol in 0.1 mL of methylenechloride), RHODORSIL® PHOTOINITIATOR 2074 (2.55E-3 g, 2.51E-6 mol in 0.1mL of methylene chloride) and 6.12 g of toluene to form the varnishsolution. The varnish solution was filtered through a 5-micron porefilter prior to use.

Example V12

HxNB (42.03 g, 0.24 mol) and (SiX) (7.97 g, 0.026 mol) were weighed outinto a glass vial. To this solution of monomers were added twoantioxidants, Ciba® IRGANOX® 1076 (0.5 g) and Ciba® IRGAFOS® 168 (0.125g) to form a monomer-antioxidant solution. To 30 g of the above preparedcopolymer P9 solution, were added 1.0 g of the monomer-antioxidantsolution, Pd(PCy3)2(OAc)2 (Pd785) (1.65E-4 g, 2.10E-7 mol in 0.1 mL ofmethylene chloride), RHODORSIL® PHOTOINITIATOR 2074 (8.51E-4 g, 8.38E-7mol in 0.1 mL of methylene chloride) and 5.0 g of toluene and to formthe varnish solution.

Example V13

HxNB (42.03 g, 0.24 mol) and (SiX) (7.97 g, 0.026 mol) were weighed outinto a glass vial. To this solution of monomers were added twoantioxidants, Ciba® IRGANOX® 1076 (0.5 g) and Ciba® IRGAFOS® 168 (0.125g) to form a monomer-antioxidant solution. To 30 g of the above preparedcopolymer P14 solution, were added 2.0 g of the monomer-antioxidantsolution, Pd(PCy₃)₂(OAc)₂ (Pd785) (3.29E-4 g, 4.19E-7 mol in 0.1 mL ofmethylene chloride), TAG-372R photo acid generator (CAS 193957-54-9,available from Toyo Ink Mfg. Co., Ltd., Tokyo, Japan) (7.63E-4 g,8.38E-6 mol in 0.1 mL of methylene chloride) and 10.0 g of toluene toform the varnish solution. The varnish solution V13 was poured onto a 4″SiO2 coated wafer and cured to form dry film. The Tg (based onthermomechanical analysis (TMA) measurement) of this polymer was 251° C.

Example V38

HxNB (16.64 g, 0.093 mol) and bis-Norbornenemethoxy dimethylsilane (SiX,CAS 376609-87-9) (33.36 g, 0.110 mol) were weighed out into a glassvial. To this solution of monomers were added two antioxidants, Ciba®IRGANOX® 1076 (0.5 g) and Ciba® IRGAFOS® 168 (0.125 g) (both availablefrom Ciba Specialty Chemicals Corporation, Tarrytown, N.Y.) to form amonomer-antioxidant solution. To 30.0 g of the above prepared P3copolymer solution, were added 2.16 g of the monomer-antioxidantsolution, Pd(PCy₃)₂(OAc)₂ (Pd785) (1.47E-3 g, 1.88E-6 mol in 0.1 mL ofmethylene chloride) and RHODORSIL® PHOTOINITIATOR 2074 (CAS 178233-72-2,available from Rhodia Inc, Cranbury, N.J.) (7.67E-3 g, 7.54E-6 mol in0.1 mL of methylene chloride) to form a varnish solution. The varnishsolution was filtered through a 0.2-micron pore filter prior to use.

Example V39

HxNB (16.64 g, 0.093 mol) and bis-Norbornenemethoxy dimethylsilane (SiX,CAS 376609-87-9) (33.36 g, 0.110 mol) were weighed out into a glassvial. To this solution of monomers were added two antioxidants, Ciba®IRGANOX® 1076 (0.5 g) and Ciba® IRGAFOS® 168 (0.125 g) (both availablefrom Ciba Specialty Chemicals Corporation, Tarrytown, N.Y.) to form amonomer-antioxidant solution. To 30.0 g of the above prepared P34copolymer solution, were added 2.16 g of the monomer-antioxidantsolution, Pd(PCy₃)₂(OAc)₂ (Pd785) (1.47E-3 g, 1.88E-6 mol in 0.1 mL ofmethylene chloride) and RHODORSIL® PHOTOINITIATOR 2074 (CAS 178233-72-2,available from Rhodia Inc, Cranbury, N.J.) (7.67E-3 g, 7.54E-6 mol in0.1 mL of methylene chloride) to form a varnish solution. The varnishsolution was filtered through a 0.2-micron pore filter prior to use.

Example V40

HxNB (16.64 g, 0.093 mol) and bis-Norbornenemethoxy dimethylsilane (SiX,CAS 376609-87-9) (33.36 g, 0.110 mol) were weighed out into a glassvial. To this solution of monomers were added two antioxidants, Ciba®IRGANOX® 1076 (0.5 g) and Ciba® IRGAFOS® 168 (0.125 g) (both availablefrom Ciba Specialty Chemicals Corporation, Tarrytown, N.Y.) to form amonomer-antioxidant solution. To 30.0 g of the above prepared P12copolymer solution, were added 2.16 g of the monomer-antioxidantsolution, Pd(PCy₃)₂(OAc)₂ (Pd785) (1.47E-3 g, 1.88E-6 mol in 0.1 mL ofmethylene chloride), DBA (CAS 76275-14-4, available from Kawasaki-kaseiCo., Ltd., Kanagawa, Japan) (4.86E-2 g, 1.51E-4 mol in 0.1 mL ofmethyllene chloride) and RHODORSIL® PHOTOINITIATOR 2074 (CAS178233-72-2, available from Rhodia Inc, Cranbury, N.J.) (7.67E-3 g,7.54E-6 mol in 0.1 mL of methylene chloride) to form a varnish solution.The varnish solution was filtered through a 0.2-micron pore filter priorto use.

Example V41

HxNB (16.64 g, 0.093 mol) and bis-Norbornenemethoxy dimethylsilane (SiX,CAS 376609-87-9) (33.36 g, 0.110 mol) were weighed out into a glassvial. To this solution of monomers were added two antioxidants, Ciba®IRGANOX® 1076 (0.5 g) and Ciba® IRGAFOS® 168 (0.125 g) (both availablefrom Ciba Specialty Chemicals Corporation, Tarrytown, N.Y.) to form amonomer-antioxidant solution. To 30.0 g of the above prepared P16copolymer solution, were added 2.16 g of the monomer-antioxidantsolution, Pd(PCy₃)₂(OAc)₂ (Pd785) (1.47E-3 g, 1.88E-6 mol in 0.1 mL ofmethylene chloride) and RHODORSIL® PHOTOINITIATOR 2074 (CAS 178233-72-2,available from Rhodia Inc, Cranbury, N.J.) (7.67E-3 g, 7.54E-6 mol in0.1 mL of methylene chloride) to form a varnish solution. The varnishsolution was filtered through a 0.2-micron pore filter prior to use.

Example V42

HxNB (16.64 g, 0.093 mol) and bis-Norbornenemethoxy dimethylsilane (SiX,CAS 376609-87-9) (33.36 g, 0.110 mol) were weighed out into a glassvial. To this solution of monomers were added two antioxidants, Ciba®IRGANOX® 1076 (0.5 g) and Ciba® IRGAFOS® 168 (0.125 g) (both availablefrom Ciba Specialty Chemicals Corporation, Tarrytown, N.Y.) to form amonomer-antioxidant solution. To 30.0 g of the above prepared P17copolymer solution, were added 2.16 g of the monomer-antioxidantsolution, Pd(PCy₃)₂(OAc)₂ (Pd785) (1.47E-3 g, 1.88E-6 mol in 0.1 mL ofmethylene chloride) and RHODORSIL® PHOTOINITIATOR 2074 (CAS 178233-72-2,available from Rhodia Inc, Cranbury, N.J.) (7.67E-3 g, 7.54E-6 mol in0.1 mL of methylene chloride) to form a varnish solution. The varnishsolution was filtered through a 0.2-micron pore filter prior to use.

Example V43

HxNB (16.64 g, 0.093 mol) and bis-Norbornenemethoxy dimethylsilane (SiX,CAS 376609-87-9) (33.36 g, 0.110 mol) were weighed out into a glassvial. To this solution of monomers were added two antioxidants, Ciba®IRGANOX® 1076 (0.5 g) and Ciba® IRGAFOS® 168 (0.125 g) (both availablefrom Ciba Specialty Chemicals Corporation, Tarrytown, N.Y.) to form amonomer-antioxidant solution. To 30.0 g of the above prepared P18copolymer solution, were added 2.16 g of the monomer-antioxidantsolution, Pd(PCy₃)₂(OAc)₂ (Pd785) (1.47E-3 g, 1.88E-6 mol in 0.1 mL ofmethylene chloride) and RHODORSIL® PHOTOINITIATOR 2074 (CAS 178233-72-2,available from Rhodia Inc, Cranbury, N.J.) (7.67E-3 g, 7.54E-6 mol in0.1 mL of methylene chloride) to form a varnish solution. The varnishsolution was filtered through a 0.2-micron pore filter prior to use.

Example V44

Bis-Norbornenemethoxy dimethylsilane (SiX, CAS 376609-87-9) (50.0 g,0.164 mol) were weighed out into a glass vial. To this solution ofmonomers were added two antioxidants, Ciba® IRGANOX® 1076 (0.5 g) andCiba® IRGAFOS® 168 (0.125 g) (both available from Ciba SpecialtyChemicals Corporation, Tarrytown, N.Y.) to form a monomer-antioxidantsolution. To 30.0 g of the above prepared P19 copolymer solution, wereadded 1.44 g of the monomer-antioxidant solution, Pd(P(i-Pr)₃)₂(OAc)₂(Pd545) (1.02E-3 g, 1.88E-6 mol in 0.1 mL of methylene chloride) andRHODORSIL® PHOTOINITIATOR 2074 (CAS 178233-72-2, available from RhodiaInc, Cranbury, N.J.) (7.67E-3 g, 7.54E-6 mol in 0.1 mL of methylenechloride) to form a varnish solution. The varnish solution was filteredthrough a 0.2-micron pore filter prior to use.

Example V45

Bis-Norbornenemethoxy dimethylsilane (SiX, CAS 376609-87-9) (50.0 g,0.164 mol) were weighed out into a glass vial. To this solution ofmonomers were added two antioxidants, Ciba® IRGANOX® 1076 (0.5 g) andCiba® IRGAFOS® 168 (0.125 g) (both available from Ciba SpecialtyChemicals Corporation, Tarrytown, N.Y.) to form a monomer-antioxidantsolution. To 30.0 g of the above prepared P20 copolymer solution, wereadded 1.44 g of the monomer-antioxidant solution, Pd(P(i-Pr)₃)₂(OAc)₂(Pd545) (1.02E-3 g, 1.88E-6 mol in 0.1 mL of methylene chloride) andRHODORSIL® PHOTOINITIATOR 2074 (CAS 178233-72-2, available from RhodiaInc, Cranbury, N.J.) (7.67E-3 g, 7.54E-6 mol in 0.1 mL of methylenechloride) to form a varnish solution. The varnish solution was filteredthrough a 0.2-micron pore filter prior to use.

Example V46

Bis-Norbornenemethoxy dimethylsilane (SiX, CAS 376609-87-9) (50.0 g,0.164 mol) were weighed out into a glass vial. To this solution ofmonomers were added two antioxidants, Ciba® IRGANOX® 1076 (0.5 g) andCiba® IRGAFOS® 168 (0.125 g) (both available from Ciba SpecialtyChemicals Corporation, Tarrytown, N.Y.) to form a monomer-antioxidantsolution. To 30.0 g of the above prepared P21 copolymer solution, wereadded 1.44 g of the monomer-antioxidant solution, Pd(P(i-Pr)₃)₂(OAc)₂(Pd545) (1.02E-3 g, 1.88E-6 mol in 0.1 mL of methylene chloride) andRHODORSIL® PHOTOINITIATOR 2074 (CAS 178233-72-2, available from RhodiaInc, Cranbury, N.J.) (7.67E-3 g, 7.54E-6 mol in 0.1 mL of methylenechloride) to form a varnish solution. The varnish solution was filteredthrough a 0.2-micron pore filter prior to use.

Example V47

HxNB (16.64 g, 0.093 mol) and bis-Norbornenemethoxy dimethylsilane (SiX,CAS 376609-87-9) (33.36 g, 0.110 mol) were weighed out into a glassvial. To this solution of monomers were added two antioxidants, Ciba®IRGANOX® 1076 (0.5 g) and Ciba® IRGAFOS® 168 (0.125 g) (both availablefrom Ciba Specialty Chemicals Corporation, Tarrytown, N.Y.) to form amonomer-antioxidant solution. To 30.0 g of the above prepared P17copolymer solution, were added 2.16 g of the monomer-antioxidantsolution, Pd(PCy₃)₂(OAc)₂ (Pd785) (1.47E-3 g, 1.88E-6 mol in 0.1 mL ofmethylene chloride) and TAG-372R photo acid generator (CAS 193957-54-9,available from Toyo Ink Mfg. Co., Ltd., Tokyo, Japan) (6.86E-3 g,7.54E-6 mol in 0.1 mL of methylene chloride) to form a varnish solution.The varnish solution was filtered through a 0.2-micron pore filter priorto use.

Example V48

Bis-Norbornenemethoxy dimethylsilane (SiX, CAS 376609-87-9) (50.0 g,0.164 mol) were weighed out into a glass vial. To this solution ofmonomers were added two antioxidants, Ciba® IRGANOX® 1076 (0.5 g) andCiba® IRGAFOS® 168 (0.125 g) (both available from Ciba SpecialtyChemicals Corporation, Tarrytown, N.Y.) to form a monomer-antioxidantsolution. To 30.0 g of the above prepared P20 copolymer solution, wereadded 1.44 g of the monomer-antioxidant solution, Pd(P(i-Pr)₃)₂(OAc)₂(Pd545) (1.02E-3 g, 1.88E-6 mol in 0.1 mL of methylene chloride) andTAG-372R photo acid generator (CAS 193957-54-9, available from Toyo InkMfg. Co., Ltd., Tokyo, Japan) (6.86E-3 g, 7.54E-6 mol in 0.1 mL ofmethylene chloride) to form a varnish solution. The varnish solution wasfiltered through a 0.2-micron pore filter prior to use.

Example V63

Bis-Norbornenemethoxy dimethylsilane (SiX, CAS 376609-87-9) (50.0 g,0.164 mol) were weighed out into a glass vial. To this solution ofmonomers were added two antioxidants, Ciba® IRGANOX® 1076 (0.5 g) andCiba® IRGAFOS® 168 (0.125 g) (both available from Ciba SpecialtyChemicals Corporation, Tarrytown, N.Y.) to form a monomer-antioxidantsolution. To 30.0 g of the above prepared P24 copolymer solution, wereadded 1.44 g of the monomer-antioxidant solution, Pd(PCy₃)₂(OAc)₂(Pd785) (1.47E-3 g, 1.88E-6 mol in 0.1 mL of methylene chloride) andRHODORSIL® PHOTOINITIATOR 2074 (CAS 178233-72-2, available from RhodiaInc, Cranbury, N.J.) (7.67E-3 g, 7.54E-6 mol in 0.1 mL of methylenechloride) to form a varnish solution. The varnish solution was filteredthrough a 0.2-micron pore filter prior to use.

Example V64

Trimethoxysilyl ethyl norbornene (TMSENB, CAS 68245-19-2) (20.2 g,0.0834 mol) and bis-Norbornenemethoxy dimethylsilane (SiX, CAS376609-87-9) (29.80 g, 0.0979 mol) were weighed out into a glass vial.To this solution of monomers were added two antioxidants, Ciba® IRGANOX®1076 (0.5 g) and Ciba® IRGAFOS® 168 (0.125 g) (both available from CibaSpecialty Chemicals Corporation, Tarrytown, N.Y.) to form amonomer-antioxidant solution. To 30.0 g of the above prepared P26copolymer solution, were added 2.16 g of the monomer-antioxidantsolution, Pd(PCy₃)₂(OAc)₂ (Pd785) (1.47E-3 g, 1.88E-6 mol in 0.1 mL ofmethylene chloride) and RHODORSIL® PHOTOINITIATOR 2074 (CAS 178233-72-2,available from Rhodia Inc, Cranbury, N.J.) (7.67E-3 g, 7.54E-6 mol in0.1 mL of methylene chloride) to form a varnish solution. The varnishsolution was filtered through a 0.2-micron pore filter prior to use.

Example V65

Trimethoxysilyl ethyl norbornene (TMSENB, CAS 68245-19-2) (20.2 g,0.0834 mol) and bis-Norbornenemethoxy dimethylsilane (SiX, CAS376609-87-9) (29.80 g, 0.0979 mol) were weighed out into a glass vial.To this solution of monomers were added two antioxidants, Ciba® IRGANOX®1076 (0.5 g) and Ciba® IRGAFOS® 168 (0.125 g) (both available from CibaSpecialty Chemicals Corporation, Tarrytown, N.Y.) to form amonomer-antioxidant solution. To 30.0 g of the above prepared P14copolymer solution, were added 2.16 g of the monomer-antioxidantsolution, Pd(PCy₃)₂(OAc)₂ (Pd785) (1.47E-3 g, 1.88E-6 mol in 0.1 mL ofmethylene chloride) and RHODORSIL® PHOTOINITIATOR 2074 (CAS 178233-72-2,available from Rhodia Inc, Cranbury, N.J.) (7.67E-3 g, 7.54E-6 mol in0.1 mL of methylene chloride) to form a varnish solution. The varnishsolution was filtered through a 0.2-micron pore filter prior to use.

Example V66

To 5 g of P14 copolymer were added 20 g of Mesitylene, IRGANOX® 1076(0.05 g), Ciba® IRGAFOS® 168 (1.25E-2 g) (both available from CibaSpecialty Chemicals Corporation, Tarrytown, N.Y.) and RHODORSIL®PHOTOINITIATOR 2074(CAS 178233-72-2, available from Rhodia Inc.,Cranbury, N.J.) (4.0E-3 g in 0.1 mL of methylene chloride) to form avarnish solution. The varnish solution was filtered through a 0.2-micronpore filter prior to use.

Tables 2, 3 and 4 provide a summary of the composition of each varnishsolution discussed above:

TABLE 2 Polymer Norbornene monomers matrix/ Mon 1 Mon 2 PAG weight (mol%) (mol %) Wt. Pd-785 Wt./mol R or T^(†) V1 P1 (3 g) HxNB SiX (10) 3 g4.94E−4 g 2.55E−3 g R (90) (6.29E−7 mol) (2.51E−6 mol) V2 P2 (3 g) N/ASiX (100) 3 g 3.10E−4 g 1.60E−3 g R (3.94E−7 mol) (1.58E−6 mol) V3 P3 (1g) HxNB SiX (10) 3 g 4.93E−4 g 2.55E−3 g R P4 (2 g) (90) (6.28E−7 mol)(2.51E−6 mol) V4 P3 (1.5 g) HxNB SiX (10) 3 g 4.93E−4 g 2.55E−3 g R P4(1.5 g) (90) (6.28E−7 mol) (2.51E−6 mol) V5 P3 (2 g) HxNB SiX (10) 3 g4.93E−4 g 2.55E−3 g R P4 (1.0 g) (90) (6.28E−7 mol) (2.51E−6 mol) V6 P3(3 g) HxNB SiX (10) 3 g 4.93E−4 g 2.55E−3 g R (90) (6.28E−7 mol)(2.51E−6 mol) V7 P3 (1.5 g) HxNB TMSEN 3 g 5.02E−4 g 2.59E−3 g R P4 (1.5g) (90) B (10) (6.39E−7 mol) (2.55E−6 mol) V8 P5 (1.8 g) HxNB SiX (10)3.1 g   3.85E−4 g 1.99E−3 g R (90) (4.91E−7 mol) (1.96E−6 mol) V9 P6(.92 g) HxNB SiX (10) 1.5 g   2.52E−4 g 1.30E−3 g R (90) (3.21E−7 mol)(1.28E−6 mol) V10 P3 (2 g) HxNB SiX (10) 2.4 g   3.95E−4 g 2.55E−3 g R(90) (5.03E−7 mol) (2.51E−6 mol) V11 P8 (2 g) HxNB SiX (10) 2.4 g  3.95E−4 g 2.55E−3 g R (90) (5.03E−7 mol) (2.51E−6 mol) V12 P9 (3 g) HxNBSiX (10) 1 g 1.65E−4 g 8.51E−4 g R (90) (2.10E−7 mol) (8.38E−7 mol) V13P14 (3 g) HxNB SiX (10) 2 g 3.29E−4 g 7.63E−4 g T (90) (4.19E−7 mol)(8.38E−6 mol)

TABLE 3 Polymer Norbornene monomers matrix/ Mon 1 Mon 2 Pd-785 or PAGweight (mol %) (mol %) Wt. Pd-545 Wt./mol R or T^(†) V38 P3 (3 g) HxNBSiX 2.16 g Pd-785  7.67E−3 g R (Hx/diPh) (46) (54)  1.47E−3 g (7.54E−6mol) (1.88E−6 mol) V39 P34 (9 g) HxNB SiX 2.16 g Pd-785  7.67E−3 g R(Hx/diPh/ (46) (54)  1.47E−3 g (7.54E−6 mol) TMSE) (1.88E−6 mol) V40 P12(9 g) HxNB SiX 2.16 g Pd-785  7.67E−3 g R (Hx/diPh) (46) (54)  1.47E−3 g(7.54E−6 mol) (1.88E−6 mol) V41 P16 (9 g) Hx/NB SiX 2.16 g Pd-785 7.67E−3 g R (Bu/PE) (46) (54)  1.47E−3 g (7.54E−6 mol) (1.88E−6 mol)V42 P17 (9 g) HxNB SiX 2.16 g Pd-785  7.67E−3 g R (Hx/PE) (46) (54) 1.47E−3 g (7.54E−6 mol) (1.88E−6 mol) V43 P18 (9 g) HxNB SiX 2.16 gPd-785  7.67E−3 g R (De/PE) (46) (54)  1.47E−3 g (7.54E−6 mol) (1.88E−6mol) V44 P19 (9 g) N/A SiX (100) 1.44 g Pd-545  7.67E−3 g R (Bz) 1.02E−3 g (7.54E−6 mol) (1.88E−6 mol) V45 P20 (9 g) N/A SiX (100) 1.44g Pd-545  7.67E−3 g R (Hx/Bz)  1.02E−3 g (7.54E−6 mol) (1.88E−6 mol) V46P21 (9 g) N/A SiX (100) 1.44 g Pd-545  7.67E−3 g R (De/Bz)  1.02E−3 g(7.54E−6 mol) (1.88E−6 mol) V47 P17 (9 g) HxNB SiX 2.16 g Pd-785 6.86E−3 g T (Hx/PE) (46) (54)  1.47E−3 g (7.54E−6 mol) (1.88E−6 mol)V48 P20 (9 g) N/A SiX (100) 1.44 g Pd-545  6.86E−3 g T (Hx/Bz)  1.02E−3g (7.54E−6 mol) (1.88E−6 mol)

TABLE 4 Polymer Norbornene monomers matrix/ Mon 1 Mon 2 PAG weight (mol%) (mol %) Wt. Pd-785 Wt./mol R or T^(†) V63 P24 (9 g) N/A SiX (100)1.44 g  1.47E−3 g  7.67E−3 g R De/AGE (1.88E−6 mol) (7.54E−6 mol) V64P26 (9 g) TMSE SiX 2.16 g  1.47E−3 g  7.67E−3 g R Hx/TMSE (46) (54)(1.88E−6 mol) (7.54E−6 mol) V65 P14 (9 g) TMSE SiX 2.16 g  1.47E−3 g 7.67E−3 g R Hx/diPh (46) (54) (1.88E−6 mol) (7.54E−6 mol) V66 P14 (5 g)— — — —  4.00E−3 g R (3.94E−6 mol) ^(†)R indicates Rhodorsil 2074 wasused and T indicates TAG-372R

Examples V21-V31, V51-V55, V61 and V62

Examples V21-V31, V51-V55, V61 and V62 demonstrate the formulation ofvarnish solutions encompassing matrix polymers, an acid generator,optional antioxidants and solvents in accordance with embodiments of thepresent invention. It will be noted that as each of the varnishsolutions exemplified below incorporates a photo sensitive material,such solutions were formulated under yellow light.

Example V21

To 5 g of P12 copolymer were added 20 g of Mesitylene, 0.05 g of Irganox1076, 0.0125 g of Irgafos 168 and RHODORSIL® PHOTOINITIATOR 2074 (CAS178233-72-2, available from Rhodia Inc, Cranbury, N.J.) (4.0E-3 g in 0.1mL of methylene chloride) to form a varnish solution. The varnishsolution was filtered through a 0.2-micron pore filter prior to use.

Example V22

To 5 g of P13 copolymer were added 20 g of Mesitylene, 0.05 g of Irganox1076, 0.0125 g of Irgafos 168 and RHODORSIL® PHOTOINITIATOR 2074 (CAS178233-72-2, available from Rhodia Inc, Cranbury, N.J.) (4.0E-3 g in 0.1mL of methylene chloride) to form a vanish solution. The varnishsolution was filtered through a 0.2-micron pore filter prior to use.

Example V23

To 5 g of P14 copolymer were added 20 g of Mesitylene, 0.05 g of Irganox1076, and 0.0125 g of Irgafos 168 to form a varnish solution. Thevarnish solution was filtered through a 0.2-micron pore filter prior touse.

Example V24

To 0.9 g of P11 homopolymer were added 3.6 g of Mesitylene, 9.0E-3 g ofIrganox 1076, 2.3E-3 g of Irgafos 168 and RHODORSIL® PHOTOINITIATOR 2074(CAS 178233-72-2, available from Rhodia Inc, Cranbury, N.J.) (1.1E-3 gin 0.1 mL of methylene chloride) to form a varnish solution. The varnishsolution was filtered through a 0.2-micron pore filter prior to use.

Example V25

To 0.9 g of P11 homopolymer were added 3.6 g of Mesitylene, 9.0E-3 g ofIrganox 1076, 2.3E-3 g of Irgafos 168 and RHODORSIL® PHOTOINITIATOR 2074(CAS 178233-72-2, available from Rhodia Inc, Cranbury, N.J.) (7.5E-4 gin 0.1 mL of methylene chloride) to form a varnish solution. The varnishsolution was filtered through a 0.2-micron pore filter prior to use.

Example V26

To 0.9 g of P11 homopolymer were added 3.6 g of Mesitylene, 9.0E-3 g ofIrganox 1076, 2.3E-3 g of Irgafos 168 and TAG-372R photo acid generator(dimethyl(2-(2-naphthly)-2-oxoethyl)sulfoniumtetrakis(pentafluorophenyl)borate, CAS 193957-54-9) available from ToyoInk Mfg. Co., Ltd., Tokyo, Japan) (7.5E-4 g in 0.1 mL of methylenechloride) to form a varnish solution. The varnish solution was filteredthrough a 0.2-micron pore filter prior to use.

Example V27

To 0.9 g of P11 homopolymer were added 3.6 g of Mesitylene, 9.0E-3 g ofIrganox 1076, 2.3E-3 g of Irgafos 168 and RHODORSIL® PHOTOINITIATOR 2074(CAS 178233-72-2, available from Rhodia Inc, Cranbury, N.J.) (1.1E-3 gin 0.1 mL of methylene chloride) to form a varnish solution. The varnishsolution was filtered through a 0.2-micron pore filter prior to use.

Example V28

To 0.9 g of P11 homopolymer were added 3.6 g of Mesitylene, 9.0E-3 g ofIrganox 1076, 2.3E-3 g of Irgafos 168 and TAG-372R photo acid generator(dimethyl(2-(2-naphthly)-2-oxoethyl)sulfoniumtetrakis(pentafluorophenyl)borate, CAS 193957-54-9) available from ToyoInk Mfg. Co., Ltd., Tokyo, Japan) (7.5E-4 g in 0.1 mL of methylenechloride) to form a varnish solution. The varnish solution was filteredthrough a 0.2-micron pore filter prior to use.

Example V29

To 0.9 g of P11 homopolymer were added 3.6 g of Mesitylene, 9.0E-3 g ofIrganox 1076, 2.3E-3 g of Irgafos 168 and TAG-372R photo acid generator(dimethyl(2-(2-naphthly)-2-oxoethyl)sulfoniumtetrakis(pentafluorophenyl)borate, CAS 193957-54-9) available from ToyoInk Mfg. Co., Ltd., Tokyo, Japan) (1.1E-3 g in 0.1 mL of methylenechloride) to form a varnish solution. The varnish solution was filteredthrough a 0.2-micron pore filter prior to use.

Example V30

To 0.9 g of P11 homopolymer were added 3.6 g of Mesitylene, 9.0E-3 g ofIrganox 1076, 2.3E-3 g of Irgafos 168 and RHODORSIL® PHOTOINITIATOR 2074(CAS 178233-72-2, available from Rhodia Inc, Cranbury, N.J.) (7.5E-4 gin 0.1 mL of methylene chloride) to form a varnish solution. The varnishsolution was filtered through a 0.2-micron pore filter prior to use.

Example V31

To 0.9 g of P11 homopolymer were added 3.6 g of Mesitylene, 9.0E-3 g ofIrganox 1076, 2.3E-3 g of Irgafos 168 and TAG-372R photo acid generator(dimethyl(2-(2-naphthly)-2-oxoethyl)sulfoniumtetrakis(pentafluorophenyl)borate, CAS 193957-54-9) available from ToyoInk Mfg. Co., Ltd., Tokyo, Japan) (1.1E-3 g in 0.1 mL of methylenechloride) to form a varnish solution. The varnish solution was filteredthrough a 0.2-micron

Example V51

To 4.0 g of the above prepared P15 homopolymer solution, were addedRHODORSIL® PHOTOINITIATOR 2074 (CAS 178233-72-2, available from RhodiaInc, Cranbury, N.J.) (1.56E-3 g, 1.54E-6 mol in 0.1 mL of methylenechloride) to form a varnish solution. The varnish solution was filteredthrough a 0.2-micron pore filter prior to use.

Example V52

To 4.0 g of the above prepared P15 homopolymer solution, were addedTAG-372R photo acid generator (CAS 193957-54-9, available from Toyo InkMfg. Co., Ltd., Tokyo, Japan) (1.56E-3 g, 1.54E-6 mol in 0.1 mL ofmethylene chloride) to form a varnish solution. The varnish solution wasfiltered through a 0.2-micron pore filter prior to use.

Example V53

To 4.0 g of the above prepared P15 homopolymer solution, were addedTAG-371 photo acid generator (CAS 193957-53-8, available from Toyo InkMfg. Co., Ltd., Tokyo, Japan) (1.56E-3 g, 1.54E-6 mol in 0.1 mL ofmethylene chloride) to form a varnish solution. The varnish solution wasfiltered through a 0.2-micron pore filter prior to use.

Example V54

To 4.0 g of the above prepared P15 homopolymer solution, were addedtris(4-tertbutylphenyl)sulphonium tetrakis(pentafluorophenyl)boratephoto acid generator (also referred to as “TTBPS-TPFPB,” available fromToyo Gosei Co., Ltd., Tokyo, Japan) (1.56E-3 g, 1.54E-6 mol in 0.1 mL ofmethylene chloride) to form a varnish solution. The varnish solution wasfiltered through a 0.2-micron pore filter prior to use.

Example V55

To 4.0 g of the above prepared P15 homopolymer solution, were addedNAI-105 photo acid generator (CAS 85342-62-7, available from Midorikagaku. Co., Ltd., Tokyo, Japan) (1.56E-3 g, 1.54E-6 mol in 0.1 mL ofmethylene chloride) to form a varnish solution. The varnish solution wasfiltered through a 0.2-micron pore filter prior to use.

Example V61

To 16.7 g of the above prepared P24 copolymer solution, were added twoantioxidants, Ciba® IRGANOX® 1076 (0.05 g), Ciba® IRGAFOS® 168 (1.25E-2g) (both available from Ciba Specialty Chemicals Corporation, Tarrytown,N.Y.) and RHODORSIL® PHOTOINITIATOR 2074 (CAS 178233-72-2, availablefrom Rhodia Inc, Cranbury, N.J.) (0.1 g in 0.5 mL of methylenechloride). The varnish solution was filtered through a 0.2-micron porefilter prior to use.

Example V62

To 16.7 g of the above prepared P24 copolymer solution, were added twoantioxidants, Ciba® IRGANOX® 1076 (0.05 g), Ciba® IRGAFOS® 168 (1.25E-2g) (both available from Ciba Specialty Chemicals Corporation, Tarrytown,N.Y.) and TAG-372R photo acid generator(dimethyl(2-(2-naphthly)-2-oxoethyl)sulfoniumtetrakis(pentafluorophenyl)borate, CAS No. 193957-54-9) available fromToyo Ink Mfg. Co., Ltd., Tokyo, Japan) (0.1 g in 0.5 mL of methylenechloride). The varnish solution was filtered through a 0.2-micron porefilter prior to use.

Table 5 provides a summary of the composition of each varnish solutiondiscussed above.

TABLE 5 Polymer PAG matrix/ (%) weight Species (wt) (w.r.t polymer) V21P12 (5 g) Rhodorsil 2074 4.0E−3 g 0.08 V22 P13 (5 g) Rhodorsil 20744.0E−3 g 0.08 V23 P14 (5 g) — — 0 V24 P11 (0.9 g) Rhodorsil 2074 1.1E−3g 0.13 V25 P11 (0.9 g) Rhodorsil 2074 7.5E−4 g 0.08 V26 P11 (0.9 g)TAG-372R 7.5E−4 g 0.08 V27 P11 (0.9 g) Rhodorsil 2074 1.1E−3 g 0.13 V28P11 (0.9 g) TAG-372R 7.5E−4 g 0.08 V29 P11 (0.9 g) TAG-372R 1.1E−3 g0.13 V30 P11 (0.9 g) Rhodorsil 2074 7.5E−4 g 0.08 V31 P11 (0.9 g)TAG-372R 1.1E−3 g 0.13 V51 P15 (4 g) Rhodorsil 1.56E−3 g 0.13(diPh-homo) V52 P15 (4 g) TAG-372R 1.56E−3 g 0.13 (diPh-homo) V53 P15 (4g) TAG-371 1.56E−3 g 0.13 (diPh-homo) V54 P15 (4 g) TTBPS-TPFPB 1.56E−3g 0.13 (diPh-homo) V55 P15 (4 g) NAI-105 1.56E−3 g 0.13 (diPh-homo) V61P24 (5 g) Rhodorsil 0.1 g 2.0 V62 P24 (5 g) TAG-372R 0.1 g 2.0Waveguide

Examples WG1-WG5

Examples WG1 to WG5 demonstrate the fabrication of single-layer andthree-layer waveguide structures in accordance with embodiments of thepresent invention. It will be noted that as each of the varnishsolutions used in the exemplified methods, below, of forming waveguidestructures incorporates a photo sensitive material, such structures wereformed under yellow light.

Example WG1 Formation of a Single-Layer Waveguide Structure

The appropriate filtered varnish solution was poured onto a 4″ glasswafer and spread to an essentially uniform thickness using a doctorblade. Then the coated glass wafer was placed on a vented leveling tableovernight to allow the solvents to evaporate and form an essentiallydry, solid film. The film was exposed to UV light (365 nm) through aphotomask (dose=3000 mJ) and then heated in an oven for 30 minutes at85° C. followed by heating for an additional 60 minutes at 150° C. Awaveguide pattern was visible after the first heating step.

Example WG2 Formation of a Three-Layer Waveguide Structure

Varnish solution V8 was poured onto 250-micron thick PET film and spreadto an essentially uniform thickness using a doctor blade (wetthickness=70-micron). Then Varnish solution V9 was poured onto the firstlayer and spread to an essentially uniform thickness using a doctorblade (wet thickness=80-micron). Finally the Varnish solution V8 waspoured onto the second layer and spread to an essentially uniformthickness using a doctor blade (wet thickness=80 micron). Then thecoated PET film was placed on a hot plate and was heated at 50° C. for30 minutes to allow the toluene to evaporate and form a solidaccumulated film. The film was exposed to UV light (365 nm) through apositive tone photomask (exposure dose=3000 mJ/cm²) and then placed on ahot plate for 30 minutes at 45° C. followed by a cure for 30 minutes at85° C. and for 60 minutes at 150° C., respectively. A waveguide patternwas visible after the film was placed on a hot plate at 45° C. for 10minutes. Propagation loss for this waveguide was measured using a “cutback method” and was determined to be 6.0 dB/cm.

Example WG3 Formation of a Three-Layer Waveguide Structure

The filtered Varnish solution V11 was poured onto 250-micron thick PETfilm and spread to an essentially uniform thickness using a doctor blade(wet thickness=70-micron). Then filtered Varnish solution V10 was pouredonto the first layer and spread to an essentially uniform thicknessusing a doctor blade (wet thickness=80-micron). Finally the filteredVarnish solution V11 was poured onto the second layer and spread to anessentially uniform thickness using a doctor blade (wetthickness=80-micron). Then the coated PET film was placed on a hot plateand was heated at 50° C. for 45 minutes to allow the toluene toevaporate and form a solid accumulated film. The film was exposed to UVlight (365 nm) through a positive tone photomask (exposure dose=3000mJ/cm²) and then put in an oven for 30 minutes at 50° C. followed by acure for 30 minutes at 85° C. and for 60 minutes at 150° C.,respectively. A waveguide pattern was visible after the film was placedin an oven at 50° C. for 10 minutes. Propagation loss for this waveguidewas measured using a “cut back method” and was determined to be 3.0dB/cm.

Example WG4 Formation of a Three-Layer Waveguide Structure

The Varnish solution V13 was poured onto 250-micron thick PET film andspread to an essentially uniform thickness using a doctor blade (wetthickness=70-micron). Then filtered Varnish solution V12 was poured ontothe first layer and spread to an essentially uniform thickness using adoctor blade (wet thickness=80-micron). Finally the Varnish solution V13was poured onto the second layer and spread to an essentially uniformthickness using a doctor blade (wet thickness=80-micron). Then thecoated PET film was placed on a hot plate and was heated at 50° C. for45 minutes to allow the toluene to evaporate and form a solidaccumulated film. The film was exposed to UV light (365 nm) through apositive tone photomask (exposure dose=3000 mJ/cm²) and then put in anoven for 30 minutes at 50° C. followed by a cure for 30 minutes at 85°C. and for 60 minutes at 150° C., respectively. A waveguide pattern wasvisible after the film was placed in an oven at 50° C. for 10 minutes.

Example WG5 Formation of a Three-Layer Waveguide Structure

Avatrel® 2000P solution (available from Promerus LLC, Brecksville, Ohio)was poured onto a 4″ glass wafer and spread to an essentially uniformthickness using a spin coater (wet thickness=1-micron). Then it wasplaced on a hot plate and heated at 100° C. for 10 minutes and exposedto UV light without a photomask (exposure dose 400 mJ/cm2) followed bycuring at 110° C. for 15 minutes and 160° C. for 1 hour, respectively.

Then the varnish solution V12 was poured onto the surface of the curedAvatrel 2000P layer and spread to an essentially uniform thickness usinga doctor blade (wet thickness=70-micron). Then the coated glass waferwas placed on a vented leveling table overnight to allow the solvents toevaporate and form an essentially dry solid film. The following day thesolid film formed of solution V12 was exposed to UV light (365 nm)through a photomask (exposure dose 3000 mJ/cm²) followed by aging atroom temperature for 30 minutes, curing first at 85° C. for 30 minutesand then at 150° C. for 60 minutes. A waveguide pattern was visibleafter the film was cured at 85° C. for 30 minutes.

Then a second portion of Avatrel 2000P solution was poured onto thesurface of the cured layer of varnish solution V12 and spread to anessentially uniform thickness using a spin coater (wet thickness=1micron). The coated glass wafer was placed on a hot plate and heated at100° C. for 10 minutes and exposed to UV light without a photomask(exposure dose 400 mJ/cm₂) followed by curing at 110° C. for 15 minutesand 160° C. for 1 hour, respectively. A waveguide pattern was stillvisible but the film looked brownish through the top cladding layer.

Propagation Loss Measurements

Propagation loss for each of the waveguides formed by five varnishsolutions, V3-V7, was measured using a “cut back method.” Each waveguidewas a single-layer waveguide fabricated using the method of Example WG1.Light (830 nm) generated from a LASER diode was input into a first endof the core of waveguide formed from each varnish solution through anoptical fiber, where the waveguide had a first length. The power of thelight output at an opposing, second end was measured. The waveguide wasthe “cut back” to at least two shorter lengths and the light outputmeasured at the second output end for each length.

Total optical loss for each of the measurements is:Total Optical Loss (dB)=−10 log(Pn/Po),where Pn is the measured output at the second end of the waveguide foreach of the lengths P₁, P₂, . . . P_(n), and Po is the measured outputof the of the light source at the end of the optical fiber before suchfiber is coupled to the first end of the waveguide core. The totaloptical loss is then plotted as exemplified in FIG. 11. The resultingbest straight line of this data is represented by the equation:y=mx+b,where m is the propagation loss and b is the coupling loss.

Results of Propagation Loss using the “cut back” method for each ofvarnish solutions V3-V7 is presented in Table 6, below.

TABLE 6 Varnish solution # V3 V4 V5 V6 V7 Propagation loss [dB/cm] 0.1830.157 0.112 0.087 0.474

Examples WG11-WG20

Examples WG11-WG20 demonstrate the fabrication of single-layer andthree-layer waveguide structures in accordance with embodiments of thepresent invention. Each of the varnish solutions used in the exemplifiedmethods of forming waveguide structures below incorporates a photosensitive material. Such structures were formed under yellow light.

Example WG11 Formation of a Single-Layer Waveguide Structure

The filtered varnish solution V24 was poured onto a glass substrate andspread to an essentially uniform thickness using a doctor blade. Thenthe glass substrate was placed on a vented leveling table overnight toallow the solvents to evaporate and form an essentially dry, solid film.The film was exposed to UV light (365 nm) through a photomask (UV dose;6 J/cm2) and then heated in an oven for 30 minutes at 85° C. followed byheating for an additional 60 minutes at 150° C. A waveguide pattern wasvisible after the first heating step.

Example WG12 Formation of a Single-Layer Waveguide Structure

The filtered varnish solution V25 was poured onto a 4″ SiO₂ coated waferand spread to an essentially uniform thickness using a doctor blade.Then the coated wafer was placed on a vented leveling table overnight toallow the solvents to evaporate and form an essentially dry, solid film.The film was exposed to UV light (365 nm) through a photomask (UV dose;3 J/cm2) and then heated in an oven for 30 minutes at 85° C. followed byheating for an additional 60 minutes at 150° C. A waveguide pattern wasvisible after the first heating step.

Example WG13 Formation of a Single-Layer Waveguide Structure

The filtered varnish solution V26 was poured onto a 4″ SiO₂ coated waferand spread to an essentially uniform thickness using a doctor blade.Then the coated wafer was placed on a vented leveling table overnight toallow the solvents to evaporate and form an essentially dry, solid film.The film was exposed to UV light (365 nm) through a photomask (UV dose;6 J/cm2) and then heated in an oven for 30 minutes at 85° C. followed byheating for an additional 60 minutes at 150° C. A waveguide pattern wasvisible after the first heating step.

Example WG14 Formation of a Single-Layer Waveguide Structure

The filtered varnish solution V27 was poured onto a 4″ SiO₂ coated waferand spread to an essentially uniform thickness using a doctor blade.Then the coated wafer was placed on a vented leveling table overnight toallow the solvents to evaporate and form an essentially dry, solid film.The film was exposed to UV light (365 nm) through a photomask (UV dose;3 J/cm2) and then heated in an oven for 30 minutes at 85° C. followed byheating for an additional 60 minutes at 150° C. A waveguide pattern wasvisible after the first heating step.

Example WG15 Formation of a Single-Layer Waveguide Structure

The filtered varnish solution V28 was poured onto a 4″ SiO₂ coated waferand spread to an essentially uniform thickness using a doctor blade.Then the coated wafer was placed on a vented leveling table overnight toallow the solvents to evaporate and form an essentially dry, solid film.The film was exposed to UV light (365 nm) through a photomask (UV dose;3 J/cm2) and then heated in an oven for 30 minutes at 85° C. followed byheating for an additional 60 minutes at 150° C. A waveguide pattern wasvisible after the first heating step.

Example WG16 Formation of a Single-Layer Waveguide Structure

The filtered varnish solution V29 was poured onto a 4″ SiO₂ coated waferand spread to an essentially uniform thickness using a doctor blade.Then the coated wafer was placed on a vented leveling table overnight toallow the solvents to evaporate and form an essentially dry, solid film.The film was exposed to UV light (365 nm) through a photomask (UV dose;3 J/cm2) and then heated in an oven for 30 minutes at 85° C. followed byheating for an additional 60 minutes at 150° C. A waveguide pattern wasvisible after the first heating step.

Example WG17 Formation of a Single-Layer Waveguide Structure

The filtered varnish solution V30 was poured onto a 4″ SiO₂ coated waferand spread to an essentially uniform thickness using a doctor blade.Then the coated wafer was placed on a vented leveling table overnight toallow the solvents to evaporate and form an essentially dry, solid film.The film was exposed to UV light (365 nm) through a photomask (UV dose;6 J/cm2) and then heated in an oven for 30 minutes at 85° C. followed byheating for an additional 60 minutes at 150° C. A waveguide pattern wasvisible after the first heating step.

Example WG18 Formation of a Single-Layer Waveguide Structure

The filtered varnish solution V31 was poured onto a 4″ SiO₂ coated waferand spread to an essentially uniform thickness using a doctor blade.Then the coated wafer was placed on a vented leveling table overnight toallow the solvents to evaporate and form an essentially dry, solid film.The film was exposed to UV light (365 nm) through a photomask (UV dose;6 J/cm2) and then heated in an oven for 30 minutes at 85° C. followed byheating for an additional 60 minutes at 150° C. A waveguide pattern wasvisible after the first heating step.

Example WG19 Formation of a Three-Layer Waveguide

Varnish solution V23 was poured onto 1 mm thick glass plate and spreadto an essentially uniform thickness using a doctor blade (wetthickness=70-micron). Then Varnish solution V21 was poured onto thefirst layer and spread to an essentially uniform thickness using adoctor blade (wet thickness=80-micron). Finally the Varnish solution V23was poured onto the second layer and spread to an essentially uniformthickness using a doctor blade (wet thickness=80 micron). Then thecoated glass plate was placed on a hot plate and was heated at 50° C.for 30 minutes to allow the mesitylene to evaporate and form a solidaccumulated film. The film was exposed to UV light (365 nm) through apositive tone photomask (exposure dose=3000 mJ/cm2) and heated for 30minutes at 85° C. and for 60 minutes at 150° C., respectively. Awaveguide pattern was visible after the glass plate was heated at 85° C.for 30 minutes. Propagation loss for this waveguide was measured using a“cut back method” and was determined to be 3.0 dB/cm.

Example WG20 Formation of a Three-Layer Waveguide

Varnish solution V23 was poured onto 1 mm thick glass plate and spreadto an essentially uniform thickness using a doctor blade (wetthickness=70-micron). Then Varnish solution V22 was poured onto thefirst layer and spread to an essentially uniform thickness using adoctor blade (wet thickness=80-micron). Finally the Varnish solution V23was poured onto the second layer and spread to an essentially uniformthickness using a doctor blade (wet thickness=80 micron). Then thecoated glass plate was placed on a hot plate and was heated at 50° C.for 30 minutes to allow the mesitylene to evaporate and form a solidaccumulated film. The film was exposed to UV light (365 nm) through apositive tone photomask (exposure dose=3000 mJ/cm2) and heated for 30minutes at 85° C. and for 60 minutes at 150° C., respectively. Awaveguide pattern was visible after the glass plate was heated at 85° C.for 30 minutes. Propagation loss for this waveguide was measured using a“cut back method” and was determined to be 2.0 dB/cm.

Propagation Loss Measurements

Propagation losses for each of the single-layer waveguides formed byeight varnish solutions V24-V31 and the three-layer waveguides formed bytwo varnish solutions V21-V22 for the core layer and one varnishsolution V23 for the cladding layer were measured in the same manner asexplained above.

Results of propagation loss of the single-layer waveguides are shown inTable 7, and results of propagation loss of the three-layer waveguidesare shown in Table 8 below.

TABLE 7 Varnish solution V24 V25 V26 V27 V28 V29 V30 V31 Energy of UV 63 6 3 3 3 6 6 Exposure (J/cm²) Waveguide WG11 WG12 WG13 WG14 WG15 WG16WG17 WG18 Propagation 0.6 0.3 0.4 0.4 0.4 0.2 0.5 0.2 loss [dB/cm]

TABLE 8 Varnish solution for cladding V23 V23 layer Varnish solution forcore layer V21 V22 Energy of UV Exposure 3 3 (J/cm²) Waveguide WG19 WG20Propagation loss [dB/cm] 3.0 2.0

Example WG21 Formation of a Single-Layer Waveguide Structure

The filtered varnish solution V38 was poured onto a quartz glass waferand spread to an essentially uniform thickness using a doctor blade.Then the quartz glass wafer was placed on a vented leveling tableovernight to allow the solvents to evaporate and form an essentiallydry, solid film. The film was exposed to UV light (365 nm) through aphotomask (UV dose; 3000 mJ) and then heated in an oven for 30 minutesat 45° C., 30 minutes at 85° C. followed by heating for an additional 60minutes at 150° C. A waveguide pattern was visible after the firstheating step.

Examples WG22-WG36

Examples WG22 to WG36 demonstrate the fabrication of single-layerwaveguide structure in accordance with embodiments of the presentinvention. WG22 to WG36 were prepared as WG21 above, except for changingthe varnish solution and amount of irradiation.

Table 9 provides a summary of the propagation loss for each of thesingle-layer waveguide WG21-WG36.

TABLE 9 Varnish solution V38 V39 V40 V41 V42 V43 V44 V45 Energy of 3 31.5 3 3 3 3 3 UV Exposure (J/cm²) Waveguide WG21 WG22 WG23 WG24 WG25WG26 WG27 WG28 Propagation 0.10 0.12 0.08 0.32 0.13 0.26 0.62 0.40 loss[dB/cm] Varnish solution V46 V47 V48 V51 V52 V53 V54 V55 Energy of 3 6 63 3 3 6 6 UV Exposure (J/cm²) Waveguide WG29 WG30 WG31 WG32 WG33 WG34WG35 WG36 Propagation 0.28 0.18 0.53 0.11 0.15 0.19 0.26 0.48 loss[dB/cm]

Example WG51 Formation of a Three-Layer Waveguide Structure

V61 was poured onto a 4″ glass wafer and spread to an essentiallyuniform thickness using a spin coater (wet thickness=1-micron). Then itwas placed on a hot plate and heated at 100° C. for 10 minutes andexposed to UV light without a photomask (exposure dose 400 mJ/cm2)followed by curing at 110° C. for 15 minutes and 160° C. for 1 hour,respectively.

Then the varnish solution V38 was poured onto the surface of the curedV1 layer and spread to an essentially uniform thickness using a doctorblade (wet thickness=70-micron). Then the coated glass wafer was placedon a vented leveling table overnight to allow the solvents to evaporateand form an essentially thy solid film. The following day the solid filmformed of solution V38 was exposed to UV light (365 nm) through aphotomask (exposure dose 3000 mJ/cm²) followed by aging at 45° C. for 30minutes, curing first at 85° C. for 30 minutes and then at 150° C. for60 minutes. A waveguide pattern was visible after the film was cured at85° C. for 30 minutes.

Then a second portion of V61 was poured onto the surface of the curedlayer of varnish solution V38 and spread to an essentially uniformthickness using a spin coater (wet thickness=1 micron). The coated glasswafer was placed on a hot plate and heated at 100° C. for 10 minutes andexposed to UV light without a photomask (exposure dose 400 mJ/cm₂)followed by curing at 110° C. for 15 minutes and 160° C. for 1 hour,respectively. A waveguide pattern was still visible but the film lookedbrownish through the top cladding layer.

Example WG52

A single-layer waveguide film (WG21) was peeled off from a glasssubstrate, rinsed with a plenty of water and then dried in an oven at45° C. for 1 hour.

The varnish solution V61 was poured onto a PET film and spread to anessentially uniform thickness using a doctor blade (wetthickness=50-micron) Then it was placed on a hot plate and heated at 45°C. for 10 minutes and exposed to UV light without a mask (exposure dose3000 mJ/cm2). Finally this cladding film was divided into two piecesusing a knife and they were peeled off from the PET film.

WG21 film was inserted between the above two cladding films and heatedin an oven at 150° C. for 1 hour under the pressure of 10 MPa.Propagation loss for this three-layer waveguide was measured using a“cut back method” and was determined to be 0.08 dB/cm. Adhesive strengthbetween core and cladding was determined by 90 degree peel test to be 50gf/cm.

Example WG53

A single-layer waveguide film (WG21) was peeled off from a glasssubstrate, rinsed with a plenty of water and then dried in an oven at45° C. for 1 hour.

The varnish solution V63 was poured onto a PET film and spread to anessentially uniform thickness using a doctor blade (wetthickness=50-micron). Then it was placed on a hot plate and heated at45° C. for 10 minutes and exposed to UV light without a mask (exposuredose 3000 mJ/cm2). Finally this cladding film was divided into twopieces using a knife and they were peeled off from the PET film.

WG21 film was inserted between the above two cladding films and heatedin an oven at 150° C. for 1 hour under the pressure of 10 MPa.Propagation loss for this three-layer waveguide was measured using a“cut back method” and was determined to be 0.08 dB/cm. Adhesive strengthbetween core and cladding was determined by 90 degree peel test to be 60gf/cm.

Example WG54

A single-layer waveguide film (WG21) was peeled off from a glasssubstrate, rinsed with a plenty of water and then dried in an oven at45° C. for 1 hour.

The varnish solution V64 was poured onto a PET film and spread to anessentially uniform thickness using a doctor blade (wetthickness=50-micron). Then it was placed on a hot plate and heated at45° C. for 10 minutes and exposed to UV light without a mask (exposuredose 3000 mJ/cm2). Finally this cladding film was divided into twopieces using a knife and they were peeled off from the PET film.

WG21 film was inserted between the above two cladding films and heatedin an oven at 150° C. for 1 hour under the pressure of 10 MPa.Propagation loss for this three-layer waveguide was measured using a“cut back method” and was determined to be 0.08 dB/cm. Adhesive strengthbetween core and cladding was determined by 90 degree peel test to be300 gf/cm.

Example WG55

A single-layer waveguide film (WG21) was peeled off from a glasssubstrate, rinsed with a plenty of water and then dried in an oven at45° C. for 1 hour.

The varnish solution V65 was poured onto a PET film and spread to anessentially uniform thickness using a doctor blade (wetthickness=50-micron). Then it was placed on a hot plate and heated at45° C. for 10 minutes and exposed to UV light without a mask (exposuredose 3000 mJ/cm2). Finally this cladding film was divided into twopieces using a knife and they were peeled off from the PET film.

WG21 film was inserted between the above two cladding films and heatedin an oven at 150° C. for 1 hour under the pressure of 10 MPa.Propagation loss for this three-layer waveguide was maeasured using a“cut back method” and was determined to be 0.08 dB/cm. Adhesive strengthbetween core and cladding was determined by 90 degree peel test to be200 gf/cm.

Example WG56

A single-layer waveguide film (WG32) was peeled off from a glasssubstrate, rinsed with a plenty of water and then dried in an oven at45° C. for 1 hour.

The varnish solution V66 was poured onto a PET film and spread to anessentially uniform thickness using a doctor blade (wetthickness=50-micron) Then it was placed on a hot plate and heated at 45°C. for 10 minutes and exposed to UV light without a mask (exposure dose3000 mJ/cm2). Finally this cladding film was divided into two piecesusing a knife and they were peeled off from the PET film.

WG32 film was inserted between the above two cladding films and heatedin an oven at 150° C. for 1 hour under the pressure of 10 MPa.Propagation loss for this three-layer waveguide was maeasured using a“cut back method” and was determined to be 0.12 dB/cm. Adhesive strengthbetween core and cladding was determined by 90 degree peel test to be 50gf/cm.

It will be realized that the norbornene-type polymers and/ornorbornene-type monomers described in the embodiments of the presentinvention provide optical waveguides having excellent transparency andpropagation loss.

Tables 10 and 11 provide a summary of the polymers and materials usedfor WG2-WG5, WG19-20 and WG51-56.

TABLE 10 Cladding Layer Polymer Norbornene monomers matrix/ Mon 1 Mon 2PAG Varnishes Weight (mol %) (mol %) Wt. Pd-785 Wt./mol R or T^(†) WG2V8 P5 (1.8 g) HxNB (90) SiX (10)  3.1 g  3.85E−4 g  1.99E−3 g R (4.91E−7mol) (1.96E−6 mol) WG3 V11 P7 (2 g) HxNB (90) SiX (10)  2.4 g  3.95E−4 g 2.55E−3 g R (5.03E−7 mol) (2.51E−6 mol) WG4 V13 P10 (3 g) HxNB (90) SiX(10)   2 g  3.29E−4 g  7.63E−4 g T (4.19E−7 mol) (8.38E−6 mol) WG5Avatrel 2000P WG19 V23 P14 (5 g) — — — — — — WG20 V23 P14 (5 g) — — — —— — WG51 V61 P24 — — — — 0.1 g R (5 g) WG52 V61 P24 — — — — 0.1 g R (5g) WG53 V63 P24 (9 g) N/A SiX (100) 1.44 g  1.47E−3 g (Pd-785)  7.67E−3g R De/AGE (1.88E−6 mol) (7.54E−6 mol) WG54 V64 P26 (9 g) TMSE (46) SiX(54) 2.16 g  1.47E−3 g (Pd-785)  7.67E−3 g R Hx/TMSE (1.88E−6 mol)(7.54E−6 mol) WG55 V65 P14 (9 g) TMSE (46) SiX (54) 2.16 g  1.47E−3 g(Pd-785)  7.67E−3 g R Hx/diPh (1.88E−6 mol) (7.54E−6 mol) WG56 V66 P14(5 g) — — — —  4.00E−3 g R (3.94E−6 mol) ^(†)R indicates Rhodorsil 2074was used and T indicates TAG-372R

TABLE 11 Waveguide Layer Polymer Norbornene monomers matrix/ Mon 1 Mon 2PAG Varnishes weight (mol %) (mol %) Wt. Pd-785 Wt./mol R or T^(†) WG2V9 P6 (.92 g) HxNB (90) SiX (10)  1.5 g  2.52E−4 g  1.30E−3 g R (3.21E−7mol) (1.28E−6 mol) WG3 V10 P8 (2 g) HxNB (90) SiX (10)  2.4 g  3.95E−4 g 2.55E−3 g R (5.03E−7 mol) (2.51E−6 mol) WG4 V12 P9 (3 g) HxNB (90) SiX(10)   1 g  1.65E−4 g  8.51E−4 g R (2.10E−7 mol) (8.38E−7 mol) WG5 V12P9 (3 g) HxNB (90) SiX (10)   1 g  1.65E−4 g  8.51E−4 g R (2.10E−7 mol)(8.38E−7 mol) WG19 V21 P12 (5 g) — — — —  4.00E−3 g R WG20 V22 P13 (5 g)— — — —  4.00E−3 g R WG51 V38 P3 (3 g) HxNB (46) SiX (54) 2.16 g 1.47E−3 g  7.67E−3 g R (Hx/diPh) (1.88E−6 mol) (7.54E−6 mol) WG52 V38P3 (3 g) HxNB (46) SiX (54) 2.16 g  1.47E−3 g  7.67E−3 g R (Hx/diPh)(1.88E−6 mol) (7.54E−6 mol) WG53 V38 P3 (3 g) HxNB (46) SiX (54) 2.16 g 1.47E−3 g  7.67E−3 g R (Hx/diPh) (1.88E−6 mol) (7.54E−6 mol) WG54 V38P3 (3 g) HxNB (46) SiX (54) 2.16 g  1.47E−3 g  7.67E−3 g R (Hx/diPh)(1.88E−6 mol) (7.54E−6 mol) WG55 V38 P3 (3 g) HxNB (46) SiX (54) 2.16 g 1.47E−3 g  7.67E−3 g R (Hx/diPh) (1.88E−6 mol) (7.54E−6 mol) WG56 V51P15 (4 g) — — — —  1.56E−3 g R (1.54E−6 mol) ^(†)R indicates Rhodorsil2074 was used and T indicates TAG-372R

1. An optical waveguide comprising: a waveguide layer having at least one cladding portion and at least one laterally adjacent core portion, wherein the at least one laterally adjacent core portion comprising a first polymer material comprising first repeat units, each of the first repeat units having a cleavable pendant group, and the at least one cladding portion comprising the first polymer material, where the cleavable pendant group is at least partly absent from at least some of the first repeat units such that a first refractive index of the at least one laterally adjacent core portion is higher than a second refractive index of the at least one cladding portion.
 2. The optical waveguide according to claim 1, where the first polymer material is a norbornene-type polymer.
 3. The optical waveguide of claim 1, where the first polymer material further comprises second repeat units.
 4. The optical waveguide of claim 3, where the first repeat units comprise hexyl norbornene repeat units and the second repeat units comprise diphenylmethyl norbornenemethoxy silane repeat units.
 5. The optical waveguide of claim 1, where the first polymer material further comprises repeat units of at least one monomer, the at least one monomer has a refractive index lower than the refractive index of the first repeat units having the cleavable pendant group, and the at least one cladding portion has a larger concentration of the repeat units of the at least one monomer than the at least one laterally adjacent core portion.
 6. The optical waveguide of claim 5, where the at least one monomer comprises a norbornene-type monomer.
 7. The optical waveguide of claim 5, where the at least one monomer comprises a crosslinker monomer.
 8. The optical waveguide of claim 7, where the crosslinker monomer is a norbornene-type crosslinker monomer.
 9. The optical waveguide of claim 1, where the first polymer material comprises one of a homopolymer, a copolymer and a terpolymer.
 10. The optical waveguide of claim 1, where the waveguide layer further comprises at least one of a procatalyst and a residue thereof.
 11. The optical waveguide of claim 10, where the procatalyst is represented by the formula E(R)₃)₂Pd(Q)₂, where E(R)₃ is a Group 15 neutral electron donor ligand, E is an element selected from the group consisting of elements of Group 15 of the Periodic Table, R in E(R)₃ is one of a hydrogen, an isotope thereof and a hydrocarbyl containing moiety, and Q is an anionic ligand selected from the group consisting of a carboxylate, a thiocarboxylate and a dithiocarboxylate.
 12. The optical waveguide of claim 10, where the procatalyst is represented by the formula [(E(R)₃)_(a)Pd(Q)(LB)_(b)]_(p)[WCA]_(r), where E(R)₃ is a Group 15 neutral electron donor ligand, E is a Group 15 element, and R independently is one of a hydrogen, an isotope thereof, and an anionic hydrocarbyl containing moiety, Q is an anionic ligand selected from the group consisting of a carboxylate, a thiocarboxylate and a dithiocarboxylate, LB is a Lewis base, WCA represents a weakly coordinating anion, a is an integer of 1, 2, or 3, b is an integer of 0, 1, or 2, where a+b is 1, 2, or 3, and p and r are integers that represent a number of times a palladium cation and the weakly coordinating anion are taken to balance an electronic charge on a structure of [(E(R)₃)_(a)Pd(Q)(LB)_(b)]_(p)[WCA]_(r).
 13. The optical waveguide of claim 12, where p and r are independently selected from an integer of 1 and
 2. 14. The optical waveguide of claim 1, where the waveguide layer further comprises an antioxidant.
 15. The optical waveguide of claim 1, where the cleavable pendent group comprises at least one component selected from the group consisting of —O—, Si-phenyl and —OSi—.
 16. The optical waveguide of claim 1, further comprising a cladding layer disposed over the waveguide layer.
 17. The optical waveguide of claim 16, where the cladding layer comprises a norbornene-type polymer.
 18. The optical waveguide of claim 1, further comprising a substrate supporting the waveguide layer. 